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Sample records for bunsatsu bimolecular mechanism

  1. Bimolecular reactions of carbenes: Proton transfer mechanism

    Science.gov (United States)

    Abu-Saleh, Abd Al-Aziz A.; Almatarneh, Mansour H.; Poirier, Raymond A.

    2018-04-01

    Here we report the bimolecular reaction of trifluoromethylhydroxycarbene conformers and the water-mediated mechanism of the 1,2-proton shift for the unimolecular trans-conformer by using quantum chemical calculations. The CCSD(T)/cc-pVTZ//MP2/cc-pVDZ potential-energy profile of the bimolecular reaction of cis- and trans-trifluoromethylhydroxycarbene, shows the lowest gas-phase barrier height of 13 kJ mol-1 compared to the recently reported value of 128 kJ mol-1 for the unimolecular reaction. We expect bimolecular reactions of carbene's stereoisomers will open a valuable field for new and useful synthetic strategies.

  2. Observation of correlated excitations in bimolecular collisions

    Science.gov (United States)

    Gao, Zhi; Karman, Tijs; Vogels, Sjoerd N.; Besemer, Matthieu; van der Avoird, Ad; Groenenboom, Gerrit C.; van de Meerakker, Sebastiaan Y. T.

    2018-02-01

    Although collisions between atoms and molecules are largely understood, collisions between two molecules have proven much harder to study. In both experiment and theory, our ability to determine quantum-state-resolved bimolecular cross-sections lags behind their atom-molecule counterparts by decades. For many bimolecular systems, even rules of thumb—much less intuitive understanding—of scattering cross sections are lacking. Here, we report the measurement of state-to-state differential cross sections on the collision of state-selected and velocity-controlled nitric oxide (NO) radicals and oxygen (O2) molecules. Using velocity map imaging of the scattered NO radicals, the full product-pair correlations of rotational excitation that occurs in both collision partners from individual encounters are revealed. The correlated cross sections show surprisingly good agreement with quantum scattering calculations using ab initio NO-O2 potential energy surfaces. The observations show that the well-known energy-gap law that governs atom-molecule collisions does not generally apply to bimolecular excitation processes, and reveal a propensity rule for the vector correlation of product angular momenta.

  3. Analysis of Brownian Dynamics Simulations of Reversible Bimolecular Reactions

    KAUST Repository

    Lipková, Jana

    2011-01-01

    A class of Brownian dynamics algorithms for stochastic reaction-diffusion models which include reversible bimolecular reactions is presented and analyzed. The method is a generalization of the λ-bcȳ model for irreversible bimolecular reactions which was introduced in [R. Erban and S. J. Chapman, Phys. Biol., 6(2009), 046001]. The formulae relating the experimentally measurable quantities (reaction rate constants and diffusion constants) with the algorithm parameters are derived. The probability of geminate recombination is also investigated. © 2011 Society for Industrial and Applied Mathematics.

  4. Report on result 1998. Research and development on fusion area. Part 3 (biomolecular mechanism and design); 1998 nendo seika hokokusho. Yugo ryoiki kenkyu kaihatsu daisan bunsatsu (bimolecular mechanism and design)

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1999-03-01

    An organism is a molecular mechanical system consisting of nucleic acid, peptide and protein having a self-forming and a self-repairing function. For the purpose of creating cells, tissues and molecular mechanism alternating these biological functions, their basic technology was developed. Concretely, studies were made on three-dimensional cellular structural module engineering and biomolecular mechanism and design. Studies on biological soft tissue resulted in success by giving atmospheric glow discharge treatment to the inner surface of a tubular PVC. An artificial vitreous body was created using PVA hydrogels. In addition, liver cells were successfully cultured for the first time in the world. Studies on biological hard tissue revealed that osteopontin plays a role of a trigger for the initial differentiation of the osteoblast cell. Further, a basic experiment was carried out on the initial response of the cartilage cell. In the research on the molecular mechanism, examination was made on the mechanism of a double-head molecular motor. Examination was also made on the adjustment of the hydrogenase LB film as an electricity/hydrogen energy conversion element and on the biomolecular mechanism and design. (NEDO)

  5. Theoretical study on the mechanism of the reaction of FOX-7 with OH and NO2 radicals: bimolecular reactions with low barrier during the decomposition of FOX-7

    Science.gov (United States)

    Zhang, Ji-Dong; Zhang, Li-Li

    2017-12-01

    The decomposition of 1,1-diamino-2,2-dinitroethene (FOX-7) attracts great interests, while the studies on bimolecular reactions during the decomposition of FOX-7 are scarce. This study for the first time investigated the bimolecular reactions of OH and NO2 radicals, which are pyrolysis products of ammonium perchlorate (an efficient oxidant usually used in solid propellant), with FOX-7 by computational chemistry methods. The molecular geometries and energies were calculated using the (U)B3LYP/6-31++G(d,p) method. The rate constants of the reactions were calculated by canonical variational transition state theory. We found three mechanisms (H-abstraction, OH addition to C and N atom) for the reaction of OH + FOX-7 and two mechanisms (O abstraction and H abstraction) for the reaction of NO2 + FOX-7. OH radical can abstract H atom or add to C atom of FOX-7 with barriers near to zero, which means OH radical can effectively degrade FOX-7. The O abstraction channel of the reaction of NO2 + FOX-7 results in the formation of NO3 radical, which has never been detected experimentally during the decomposition of FOX-7.

  6. RPMDrate: Bimolecular chemical reaction rates from ring polymer molecular dynamics

    KAUST Repository

    Suleimanov, Yu.V.

    2013-03-01

    We present RPMDrate, a computer program for the calculation of gas phase bimolecular reaction rate coefficients using the ring polymer molecular dynamics (RPMD) method. The RPMD rate coefficient is calculated using the Bennett-Chandler method as a product of a static (centroid density quantum transition state theory (QTST) rate) and a dynamic (ring polymer transmission coefficient) factor. The computational procedure is general and can be used to treat bimolecular polyatomic reactions of any complexity in their full dimensionality. The program has been tested for the H+H2, H+CH 4, OH+CH4 and H+C2H6 reactions. © 2012 Elsevier B.V. All rights reserved.

  7. RPMDrate: Bimolecular chemical reaction rates from ring polymer molecular dynamics

    KAUST Repository

    Suleimanov, Yu.V.; Allen, J.W.; Green, W.H.

    2013-01-01

    We present RPMDrate, a computer program for the calculation of gas phase bimolecular reaction rate coefficients using the ring polymer molecular dynamics (RPMD) method. The RPMD rate coefficient is calculated using the Bennett-Chandler method as a product of a static (centroid density quantum transition state theory (QTST) rate) and a dynamic (ring polymer transmission coefficient) factor. The computational procedure is general and can be used to treat bimolecular polyatomic reactions of any complexity in their full dimensionality. The program has been tested for the H+H2, H+CH 4, OH+CH4 and H+C2H6 reactions. © 2012 Elsevier B.V. All rights reserved.

  8. The influence of the "cage effect" on the mechanism of reversible bimolecular multistage chemical reactions in solutions.

    Science.gov (United States)

    Doktorov, Alexander B

    2015-08-21

    Manifestations of the "cage effect" at the encounters of reactants are theoretically treated by the example of multistage reactions in liquid solutions including bimolecular exchange reactions as elementary stages. It is shown that consistent consideration of quasi-stationary kinetics of multistage reactions (possible only in the framework of the encounter theory) for reactions proceeding near reactants contact can be made on the basis of the concepts of a "cage complex." Though mathematically such a consideration is more complicated, it is more clear from the standpoint of chemical notions. It is established that the presence of the "cage effect" leads to some important effects not inherent in reactions in gases or those in solutions proceeding in the kinetic regime, such as the appearance of new transition channels of reactant transformation that cannot be caused by elementary event of chemical conversion for the given mechanism of reaction. This results in that, for example, rate constant values of multistage reaction defined by standard kinetic equations of formal chemical kinetics from experimentally measured kinetics can differ essentially from real values of these constants.

  9. Construction of a bimolecular fluorescence complementation (BiFC ...

    African Journals Online (AJOL)

    Protein–protein interactions are essential for signal transduction in cells. Bimolecular fluorescence complementation (BiFC) is a novel technology that utilises green fluorescent proteins to visualize protein–protein interactions and subcellular protein localisation. BiFC based on pSATN vectors are a good system for ...

  10. Does increasing pressure always accelerate the condensed material decay initiated through bimolecular reactions? A case of the thermal decomposition of TKX-50 at high pressures.

    Science.gov (United States)

    Lu, Zhipeng; Zeng, Qun; Xue, Xianggui; Zhang, Zengming; Nie, Fude; Zhang, Chaoyang

    2017-08-30

    Performances and behaviors under high temperature-high pressure conditions are fundamentals for many materials. We study in the present work the pressure effect on the thermal decomposition of a new energetic ionic salt (EIS), TKX-50, by confining samples in a diamond anvil cell, using Raman spectroscopy measurements and ab initio simulations. As a result, we find a quadratic increase in decomposition temperature (T d ) of TKX-50 with increasing pressure (P) (T d = 6.28P 2 + 12.94P + 493.33, T d and P in K and GPa, respectively, and R 2 = 0.995) and the decomposition under various pressures initiated by an intermolecular H-transfer reaction (a bimolecular reaction). Surprisingly, this finding is contrary to a general observation about the pressure effect on the decomposition of common energetic materials (EMs) composed of neutral molecules: increasing pressure will impede the decomposition if it starts from a bimolecular reaction. Our results also demonstrate that increasing pressure impedes the H-transfer via the enhanced long-range electrostatic repulsion of H +δ H +δ of neighboring NH 3 OH + , with blue shifts of the intermolecular H-bonds. And the subsequent decomposition of the H-transferred intermediates is also suppressed, because the decomposition proceeds from a bimolecular reaction to a unimolecular one, which is generally prevented by compression. These two factors are the basic root for which the decomposition retarded with increasing pressure of TKX-50. Therefore, our finding breaks through the previously proposed concept that, for the condensed materials, increasing pressure will accelerate the thermal decomposition initiated by bimolecular reactions, and reveals a distinct mechanism of the pressure effect on thermal decomposition. That is to say, increasing pressure does not always promote the condensed material decay initiated through bimolecular reactions. Moreover, such a mechanism may be feasible to other EISs due to the similar intermolecular

  11. The influence of the “cage effect” on the mechanism of reversible bimolecular multistage chemical reactions in solutions

    International Nuclear Information System (INIS)

    Doktorov, Alexander B.

    2015-01-01

    Manifestations of the “cage effect” at the encounters of reactants are theoretically treated by the example of multistage reactions in liquid solutions including bimolecular exchange reactions as elementary stages. It is shown that consistent consideration of quasi-stationary kinetics of multistage reactions (possible only in the framework of the encounter theory) for reactions proceeding near reactants contact can be made on the basis of the concepts of a “cage complex.” Though mathematically such a consideration is more complicated, it is more clear from the standpoint of chemical notions. It is established that the presence of the “cage effect” leads to some important effects not inherent in reactions in gases or those in solutions proceeding in the kinetic regime, such as the appearance of new transition channels of reactant transformation that cannot be caused by elementary event of chemical conversion for the given mechanism of reaction. This results in that, for example, rate constant values of multistage reaction defined by standard kinetic equations of formal chemical kinetics from experimentally measured kinetics can differ essentially from real values of these constants

  12. The influence of the “cage effect” on the mechanism of reversible bimolecular multistage chemical reactions in solutions

    Energy Technology Data Exchange (ETDEWEB)

    Doktorov, Alexander B., E-mail: doktorov@kinetics.nsc.ru [Voevodsky Institute of Chemical Kinetics & Combustion, Siberian Branch of the Russian Academy of Sciences, 630090 Novosibirsk, Russia and Novosibirsk State University, Novosibirsk 630090 (Russian Federation)

    2015-08-21

    Manifestations of the “cage effect” at the encounters of reactants are theoretically treated by the example of multistage reactions in liquid solutions including bimolecular exchange reactions as elementary stages. It is shown that consistent consideration of quasi-stationary kinetics of multistage reactions (possible only in the framework of the encounter theory) for reactions proceeding near reactants contact can be made on the basis of the concepts of a “cage complex.” Though mathematically such a consideration is more complicated, it is more clear from the standpoint of chemical notions. It is established that the presence of the “cage effect” leads to some important effects not inherent in reactions in gases or those in solutions proceeding in the kinetic regime, such as the appearance of new transition channels of reactant transformation that cannot be caused by elementary event of chemical conversion for the given mechanism of reaction. This results in that, for example, rate constant values of multistage reaction defined by standard kinetic equations of formal chemical kinetics from experimentally measured kinetics can differ essentially from real values of these constants.

  13. Inhomogeneous bimolecular recombination in partially crystallised tri-methylphenyl diamine glasses

    International Nuclear Information System (INIS)

    Goldie, D.M.

    2013-01-01

    The rise and fall dynamics of transient photocurrents induced by exposure to ultraviolet radiation have been analysed for a series of glassy tri-methylphenyl diamine films that have been partially crystallised by ageing under ambient conditions following vapour deposition. An inhomogeneous bimolecular recombination model that uses coupled rate equations is found to provide a consistent fit for the observed photocurrent dynamics provided the recombination rate of holes in the crystallised regions of the films is lower compared to the amorphous regions. Parameters returned by the bimolecular model are investigated as a function of the film age but are observed to be highly sensitive to the initial experimental estimates that are supplied for the effective hole recombination time. The effective hole recombination time generated by the model is found to be relatively independent of film age, however, and has a value of around 0.16 s for a carrier generation rate of 7 × 10 14 cm −3 s −1 . The effective recombination time and steady-state photoconductivity magnitudes are found to be consistent with experimental hole mobility and photo-carrier generation efficiency values that are obtained using complementary time-of-flight and charge collection experiments. - Highlights: ► Transient photocurrents in evaporated diamine films have fast and slow components. ► Transient photocurrents are modelled using inhomogeneous bimolecular recombination. ► Recombination rates differ between crystallised and amorphous film regions. ► Recombination parameters evolve with film age as the films crystallise

  14. The influence of the "cage" effect on the mechanism of reversible bimolecular multistage chemical reactions proceeding from different sites in solutions.

    Science.gov (United States)

    Doktorov, Alexander B

    2016-08-28

    Manifestations of the "cage" effect at the encounters of reactants have been theoretically treated on the example of multistage reactions (including bimolecular exchange reactions as elementary stages) proceeding from different active sites in liquid solutions. It is shown that for reactions occurring near the contact of reactants, consistent consideration of quasi-stationary kinetics of such multistage reactions (possible in the framework of the encounter theory only) can be made on the basis of chemical concepts of the "cage complex," just as in the case of one-site model described in the literature. Exactly as in the one-site model, the presence of the "cage" effect gives rise to new channels of reactant transformation that cannot result from elementary event of chemical conversion for the given reaction mechanism. Besides, the multisite model demonstrates new (as compared to one-site model) features of multistage reaction course.

  15. Uncertainty for calculating transport on Titan: A probabilistic description of bimolecular diffusion parameters

    Science.gov (United States)

    Plessis, S.; McDougall, D.; Mandt, K.; Greathouse, T.; Luspay-Kuti, A.

    2015-11-01

    Bimolecular diffusion coefficients are important parameters used by atmospheric models to calculate altitude profiles of minor constituents in an atmosphere. Unfortunately, laboratory measurements of these coefficients were never conducted at temperature conditions relevant to the atmosphere of Titan. Here we conduct a detailed uncertainty analysis of the bimolecular diffusion coefficient parameters as applied to Titan's upper atmosphere to provide a better understanding of the impact of uncertainty for this parameter on models. Because temperature and pressure conditions are much lower than the laboratory conditions in which bimolecular diffusion parameters were measured, we apply a Bayesian framework, a problem-agnostic framework, to determine parameter estimates and associated uncertainties. We solve the Bayesian calibration problem using the open-source QUESO library which also performs a propagation of uncertainties in the calibrated parameters to temperature and pressure conditions observed in Titan's upper atmosphere. Our results show that, after propagating uncertainty through the Massman model, the uncertainty in molecular diffusion is highly correlated to temperature and we observe no noticeable correlation with pressure. We propagate the calibrated molecular diffusion estimate and associated uncertainty to obtain an estimate with uncertainty due to bimolecular diffusion for the methane molar fraction as a function of altitude. Results show that the uncertainty in methane abundance due to molecular diffusion is in general small compared to eddy diffusion and the chemical kinetics description. However, methane abundance is most sensitive to uncertainty in molecular diffusion above 1200 km where the errors are nontrivial and could have important implications for scientific research based on diffusion models in this altitude range.

  16. Self-assembled tethered bimolecular lipid membranes.

    Science.gov (United States)

    Sinner, Eva-Kathrin; Ritz, Sandra; Naumann, Renate; Schiller, Stefan; Knoll, Wolfgang

    2009-01-01

    This chapter describes some of the strategies developed in our group for designing, constructing and structurally and functionally characterizing tethered bimolecular lipid membranes (tBLM). We introduce this platform as a novel model membrane system that complements the existing ones, for example, Langmuir monolayers, vesicular liposomal dispersions and bimolecular ("black") lipid membranes. Moreover, it offers the additional advantage of allowing for studies of the influence of membrane structure and order on the function of integral proteins, for example, on how the composition and organization of lipids in a mixed membrane influence the ion translocation activity of integral channel proteins. The first strategy that we introduce concerns the preparation of tethered monolayers by the self-assembly of telechelics. Their molecular architecture with a headgroup, a spacer unit (the "tether") and the amphiphile that mimics the lipid molecule allows them to bind specifically to the solid support thus forming the proximal layer of the final architecture. After fusion of vesicles that could contain reconstituted proteins from a liposomal dispersion in contact to this monolayer the tethered bimolecular lipid membrane is obtained. This can then be characterized by a broad range of surface analytical techniques, including surface plasmon spectroscopies, the quartz crystal microbalance, fluorescence and IR spectroscopies, and electrochemical techniques, to mention a few. It is shown that this concept allows for the construction of tethered lipid bilayers with outstanding electrical properties including resistivities in excess of 10 MOmega cm2. A modified strategy uses the assembly of peptides as spacers that couple covalently via their engineered sulfhydryl or lipoic acid groups at the N-terminus to the employed gold substrate, while their C-terminus is being activated afterward for the coupling of, for example, dimyristoylphosphatidylethanol amine (DMPE) lipid molecules

  17. Bimolecular reaction dynamics from photoelectron spectroscopy of negative ions

    Energy Technology Data Exchange (ETDEWEB)

    Bradforth, S.E.

    1992-11-01

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

  18. Use of X-ray diffraction, molecular simulations, and spectroscopy to determine the molecular packing in a polymer-fullerene bimolecular crystal

    KAUST Repository

    Miller, Nichole Cates

    2012-09-05

    The molecular packing in a polymer: fullerene bimolecular crystal is determined using X-ray diffraction (XRD), molecular mechanics (MM) and molecular dynamics (MD) simulations, 2D solid-state NMR spectroscopy, and IR absorption spectroscopy. The conformation of the electron-donating polymer is significantly disrupted by the incorporation of the electron-accepting fullerene molecules, which introduce twists and bends along the polymer backbone and 1D electron-conducting fullerene channels. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Use of X-ray diffraction, molecular simulations, and spectroscopy to determine the molecular packing in a polymer-fullerene bimolecular crystal

    KAUST Repository

    Miller, Nichole Cates; Cho, Eunkyung; Junk, Matthias J N; Gysel, Roman; Risko, Chad; Kim, Dongwook; Sweetnam, Sean; Miller, Chad E.; Richter, Lee J.; Kline, Regis Joseph; Heeney, Martin J.; McCulloch, Iain A.; Amassian, Aram; Acevedo-Feliz, Daniel; Knox, Christopher; Hansen, Michael Ryan; Dudenko, Dmytro V.; Chmelka, Bradley F.; Toney, Michael F.; Bré das, Jean Luc; McGehee, Michael D.

    2012-01-01

    The molecular packing in a polymer: fullerene bimolecular crystal is determined using X-ray diffraction (XRD), molecular mechanics (MM) and molecular dynamics (MD) simulations, 2D solid-state NMR spectroscopy, and IR absorption spectroscopy. The conformation of the electron-donating polymer is significantly disrupted by the incorporation of the electron-accepting fullerene molecules, which introduce twists and bends along the polymer backbone and 1D electron-conducting fullerene channels. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Bimolecular reaction dynamics from photoelectron spectroscopy of negative ions

    International Nuclear Information System (INIS)

    Bradforth, S.E.

    1992-11-01

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

  1. Very Low Rate Constants of Bimolecular CO Adsorption on Anionic Gold Clusters: Implications for Catalytic Activity

    Czech Academy of Sciences Publication Activity Database

    Balteanu, I.; Balaj, O. P.; Fox, B. S.; Beyer, M. K.; Bastl, Zdeněk; Bondybey, V. E.

    2003-01-01

    Roč. 5, - (2003), s. 1213-1218 ISSN 1463-9076 Institutional research plan: CEZ:AV0Z4040901 Keywords : bimolecular * adsorption * catalytic activity Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.959, year: 2003

  2. Bimolecular Master Equations for a Single and Multiple Potential Wells with Analytic Solutions.

    Science.gov (United States)

    Ghaderi, Nima

    2018-04-12

    The analytic solutions, that is, populations, are derived for the K-adiabatic and K-active bimolecular master equations, separately, for a single and multiple potential wells and reaction channels, where K is the component of the total angular momentum J along the axis of least moment of inertia of the recombination products at a given energy E. The analytic approach provides the functional dependence of the population of molecules on its K-active or K-adiabatic dissociation, association rate constants and the intermolecular energy transfer, where the approach may complement the usual numerical approaches for reactions of interest. Our previous work, Part I, considered the solutions for a single potential well, whereby an assumption utilized there is presently obviated in the derivation of the exact solutions and farther discussed. At the high-pressure limit, the K-adiabatic and K-active bimolecular master equations may each reduce, respectively, to the K-adiabatic and K-active bimolecular Rice-Ramsperger-Kassel-Marcus theory (high-pressure limit expressions) for bimolecular recombination rate constant, for a single potential well, and augmented by isomerization terms when multiple potential wells are present. In the low-pressure limit, the expression for population above the dissociation limit, associated with a single potential well, becomes equivalent to the usual presumed detailed balance between the association and dissociation rate constants, where the multiple well case is also considered. When the collision frequency of energy transfer, Z LJ , between the chemical intermediate and bath gas is sufficiently less than the dissociation rate constant k d ( E' J' K') for postcollision ( E' J' K), then the solution for population, g( EJK) + , above the critical energy further simplifies such that depending on Z LJ , the dissociation and association rate constant k r ( EJK), as g( EJK) + = k r ( EJK)A·BC/[ Z LJ + k d ( EJK)], where A and BC are the reactants, for

  3. Modeling Bimolecular Reactive Transport With Mixing-Limitation: Theory and Application to Column Experiments

    Science.gov (United States)

    Ginn, T. R.

    2018-01-01

    The challenge of determining mixing extent of solutions undergoing advective-dispersive-diffusive transport is well known. In particular, reaction extent between displacing and displaced solutes depends on mixing at the pore scale, that is, generally smaller than continuum scale quantification that relies on dispersive fluxes. Here a novel mobile-mobile mass transfer approach is developed to distinguish diffusive mixing from dispersive spreading in one-dimensional transport involving small-scale velocity variations with some correlation, such as occurs in hydrodynamic dispersion, in which short-range ballistic transports give rise to dispersed but not mixed segregation zones, termed here ballisticules. When considering transport of a single solution, this approach distinguishes self-diffusive mixing from spreading, and in the case of displacement of one solution by another, each containing a participant reactant of an irreversible bimolecular reaction, this results in time-delayed diffusive mixing of reactants. The approach generates models for both kinetically controlled and equilibrium irreversible reaction cases, while honoring independently measured reaction rates and dispersivities. The mathematical solution for the equilibrium case is a simple analytical expression. The approach is applied to published experimental data on bimolecular reactions for homogeneous porous media under postasymptotic dispersive conditions with good results.

  4. Bimolecular reaction dynamics from photoelectron spectroscopy of negative ions

    Energy Technology Data Exchange (ETDEWEB)

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

    1992-11-01

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

  5. Efficient Homodifunctional Bimolecular Ring-Closure Method for Cyclic Polymers by Combining RAFT and Self-Accelerating Click Reaction.

    Science.gov (United States)

    Qu, Lin; Sun, Peng; Wu, Ying; Zhang, Ke; Liu, Zhengping

    2017-08-01

    An efficient metal-free homodifunctional bimolecular ring-closure method is developed for the formation of cyclic polymers by combining reversible addition-fragmentation chain transfer (RAFT) polymerization and self-accelerating click reaction. In this approach, α,ω-homodifunctional linear polymers with azide terminals are prepared by RAFT polymerization and postmodification of polymer chain end groups. By virtue of sym-dibenzo-1,5-cyclooctadiene-3,7-diyne (DBA) as small linkers, well-defined cyclic polymers are then prepared using the self-accelerating double strain-promoted azide-alkyne click (DSPAAC) reaction to ring-close the azide end-functionalized homodifunctional linear polymer precursors. Due to the self-accelerating property of DSPAAC ring-closing reaction, this novel method eliminates the requirement of equimolar amounts of telechelic polymers and small linkers in traditional bimolecular ring-closure methods. It facilitates this method to efficiently and conveniently produce varied pure cyclic polymers by employing an excess molar amount of DBA small linkers. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Effects of geminate and bimolecular recombination on the performance of polymeric-small molecular solar cells

    Energy Technology Data Exchange (ETDEWEB)

    Schubert, Marcel; Yin, Chunhong; Castellani, Mauro; Neher, Dieter [University of Potsdam, Institute of Physics and Astronomy, 14476 Potsdam-Golm (Germany); Sellinger, Alan [IMRE, 3 Research Link, 117602 Singapore (Singapore)

    2009-07-01

    Many physical properties of organic photovoltaics are related to the nature of the geminate pair, an intermediate state that forms after dissociation of photogenerated excitons and prior to free charge carrier generation. Whereas it was found that photocurrent generation is dominated by the strong field dependent process of geminate pair dissociation, the recombination of uncorrelated free charge carriers and the formation of space charge seem to play a minor role in the prominent P3HT/PCBM combination. The situation may change, when using different D/A combinations or other soluble acceptor molecules. We present organic solar cells comprising a novel small molecule based on 2-vinyl-4,5-dicyanoimidazole (Vinazene) as acceptor and M3EH-PPV as donor. While bilayer devices show promising results with a fill factor up to 57 %, the IU-characteristics of bulk heterojunction devices are dominated by bimolecular recombination and space charge effects even at moderate illumination intensities. Photo-CELIV measurements were performed to study the bimolecular recombination in detail. By combining photo-CELIV results with PL and IU measurements we are able to analyze the interrelation of recombination losses, free charge carrier generation and exciplex formation.

  7. Real-time observation of intersystem crossing induced by charge recombination during bimolecular electron transfer reactions

    KAUST Repository

    Alsam, Amani Abdu

    2016-09-21

    Real-time probing of intersystem crossing (ISC) and triplet-state formation after photoinduced electron transfer (ET) is a particularly challenging task that can be achieved by time-resolved spectroscopy with broadband capability. Here, we examine the mechanism of charge separation (CS), charge recombination (CR) and ISC of bimolecular photoinduced electron transfer (PET) between poly[(9,9-di(3,3′-N,N’-trimethyl-ammonium) propyl fluorenyl-2,7-diyl)-alt-co-(9,9-dioctyl-fluorenyl-2,7-diyl)] diiodide salt (PFN) and dicyanobenzene (DCB) using time-resolved spectroscopy. PET from PFN to DCB is confirmed by monitoring the transient absorption (TA) and infrared spectroscopic signatures for the radical ion pair (DCB─•-PFN+•). In addition, our time-resolved results clearly demonstrate that CS takes place within picoseconds followed by CR within nanoseconds. The ns-TA data exhibit the clear spectroscopic signature of PFN triplet-triplet absorption, induced by the CR of the radical ion pairs (DCB─•-PFN+•). As a result, the triplet state of PFN (3PFN*) forms and subsequently, the ground singlet state is replenished within microseconds. © 2016

  8. Vibrational transitions in hydrogen bonded bimolecular complexes – A local mode perturbation theory approach to transition frequencies and intensities

    DEFF Research Database (Denmark)

    Mackeprang, Kasper; Kjærgaard, Henrik Grum

    2017-01-01

    The local mode perturbation theory (LMPT) model was developed to improve the description of hydrogen bonded XH-stretching transitions, where X is typically O or N. We present a modified version of the LMPT model to extend its application from hydrated bimolecular complexes to hydrogen bonded...

  9. Turing instability and bifurcation analysis in a diffusive bimolecular system with delayed feedback

    Science.gov (United States)

    Wei, Xin; Wei, Junjie

    2017-09-01

    A diffusive autocatalytic bimolecular model with delayed feedback subject to Neumann boundary conditions is considered. We mainly study the stability of the unique positive equilibrium and the existence of periodic solutions. Our study shows that diffusion can give rise to Turing instability, and the time delay can affect the stability of the positive equilibrium and result in the occurrence of Hopf bifurcations. By applying the normal form theory and center manifold reduction for partial functional differential equations, we investigate the stability and direction of the bifurcations. Finally, we give some simulations to illustrate our theoretical results.

  10. The stereodynamics of photon-initiated bimolecular reactions

    International Nuclear Information System (INIS)

    Hughes, D.W.

    1999-01-01

    This thesis concerns the stereodynamics of the product state resolved reaction: H( 2 S) + CO 2 → (HOCO) → OH(X 2 Π Ω ; v, N, f) + CO( 1 Σ + ). Translationally excited hydrogen atoms were generated from HBr and HCl precursor molecules, via polarised laser photolysis, and the Doppler lineshapes of nascent OH products were monitored using polarised laser radiation. Four different OH product channels were investigated at a collision energy of 2.5 eV, and two OH product channels were studied at a collision energy of 1.8 eV. Three main sources of product state specific information were recovered from the Doppler profiles: Differential cross-sections (DCS); Product translational energy distributions (P(f)); Product rotational angular momentum distributions. Product state specific differential cross-sections (generated through collisions at 2.5 eV) suggest that OH( 2 Π 1/2 ) products may be produced through a more 'direct' route than OH( 2 Π 3/2 ) products. Differential cross-sections recorded for OH products generated through collisions at 1.8 eV, however, imply that neither OH spin-orbit state is populated through a 'direct' mechanism. The P(f t ) distributions for all OH product channels exhibit more product translational excitation than would be expected on the basis of phase space theory. This may imply either that the lifetimes of the collision complexes are short with respect to the timescale for intramolecular internal energy randomisation, or that there are significant exit channel interactions. The polarisation of the OH rotational angular momentum distribution is seen to be highly sensitive to the rotational and spin-orbit state of the OH products, but less sensitive to the collision energy and lambda-doublet state of the OH product. This thesis outlines the scope of present day experimental stereodynamical studies of gas-phase reactions (chapter 1), the theory of vector correlations in photoninitiated bimolecular reactions (chapter 2) and the

  11. The bimolecular reaction of radiolysis product of hydrated electron at temperature up to 473K; Reaksi bimolekular antar produk radiolisis elektron terhidrasi pada temperatur hingga 473K

    Energy Technology Data Exchange (ETDEWEB)

    Sunaryo, G R [Reactor Safety Technology Research Centre, National Atomic Energy Agency, Serpong (Indonesia)

    1996-06-01

    Rate constant from the bimolecular reaction of hydrated electron was determined by using radiolysis method. The methanol solution with concentration of 5 x 10{sup -2} dm{sup 3} mol{sup -1} was used as a scavenger of H and OH radicals. The pH was kept by adding the buffer solution of 1.0 x 10{sup -3} dm{sup 3} mol{sup -1} Na{sub 2}HPO{sub 4} + 1.0 x 10{sup 4} dm{sup 3} mol{sup -1} NaH{sub 2}PO{sub 4}. The irradiation was done by using the electron beam which come from linear accelerator 28 MeV with pulse width 10ns and dose of 80 Gy per pulse. The absorbance of hydrated electron was observed at wavelength of 824 nm. By using the kinetic equation the rate reaction constants were obtained. The bimolecular reaction of hydrated electron increase with temperature up to 423K. The activation energy was 19.3 kJ mol{sup -1} and the 2 k (298K) was 1.1 x 10{sup 10} dm{sup 3} mol{sup -1}. Then this bimolecular reaction decrease at temperature higher than 423K and the rate reaction constant at 473K almost similar with that at 298K. (author)

  12. [Hypothesis and application of bimolecular marking methods in Chinese materia medica].

    Science.gov (United States)

    Huang, Lu-qi; Qian, Dan; Deng, Chao

    2015-01-01

    Based on the current shortage of genuine/false authentication and quality evaluation in the molecular identification, and the weak functional gene research in the establishment of two-dimensional molecular markering methods for Chinese materia medica, the authors proposed a new method, the bimolecular marking methods (BIMM) for Chinese materia medica, combining DNA marker and metabolomics marker, that could simultaneously research the species and quality differences at the molecular level at the present stage. The authors introduced the concept, principle, methods, and technical process of BIMM, and summarized the technical advantages in this paper. Meanwhile, the application of BIMM in the identification of multiple sources of Chinese materia medica, years-identification, different locations, elite germplasm research, discovery of new drugs resources, protection of new varieties was also discussed. As a supplement of two-dimensional molecular markering method for Chinese materia medica, BIMM would not only expand connotation of identification of Chinese materia medica but also provide another effective way for quality evaluating.

  13. Infrared laser induced organic reactions. 2. Laser vs. thermal inducment of unimolecular and hydrogen bromide catalyzed bimolecular dehydration of alcohols

    International Nuclear Information System (INIS)

    Danen, W.C.

    1979-01-01

    It has been demonstrated that a mixture of reactant molecules can be induced by pulsed infrared laser radiation to react via a route which is totally different from the pathway resulting from heating the mixture at 300 0 C. The high-energy unimolecular elimination of H 2 O from ethanol in the presence of 2-propanol and HBr can be selectively induced with a pulsed CO 2 laser in preference to either a lower energy bimolecular HBr-catalyzed dehydration or the more facile dehydration of 2-propanol. Heating the mixture resulted in the almost exclusive reaction of 2-propanol to produce propylene. It was demonstrated that the bimolecular ethanol + HBr reaction cannot be effectively induced by the infrared laser radiation as evidenced by the detrimental effect on the yield of ethylene as the HBr pressure was increased. The selective, nonthermal inducement of H 2 O elimination from vibrationally excited ethanol in the presence of 2-propanol required relatively low reactant pressures. At higher pressures intermolecular V--V energy transfer allowed the thermally more facile dehydration from 2-propanol to become the predominant reaction channel

  14. Quantum mechanical calculations of reactive scattering cross sections in bimolecular encounters

    Science.gov (United States)

    Pirkle, J. C., Jr.

    1967-01-01

    Study applies the nonequilibrium collision theory of reaction rates to the estimation of rate constants for simple reactions. The complications in the quantum mechanical description of chemical reactions and the care needed in approximating the exact wave function for the collision are shown.

  15. The natural history of biocatalytic mechanisms.

    Science.gov (United States)

    Nath, Neetika; Mitchell, John B O; Caetano-Anollés, Gustavo

    2014-05-01

    Phylogenomic analysis of the occurrence and abundance of protein domains in proteomes has recently showed that the α/β architecture is probably the oldest fold design. This holds important implications for the origins of biochemistry. Here we explore structure-function relationships addressing the use of chemical mechanisms by ancestral enzymes. We test the hypothesis that the oldest folds used the most mechanisms. We start by tracing biocatalytic mechanisms operating in metabolic enzymes along a phylogenetic timeline of the first appearance of homologous superfamilies of protein domain structures from CATH. A total of 335 enzyme reactions were retrieved from MACiE and were mapped over fold age. We define a mechanistic step type as one of the 51 mechanistic annotations given in MACiE, and each step of each of the 335 mechanisms was described using one or more of these annotations. We find that the first two folds, the P-loop containing nucleotide triphosphate hydrolase and the NAD(P)-binding Rossmann-like homologous superfamilies, were α/β architectures responsible for introducing 35% (18/51) of the known mechanistic step types. We find that these two oldest structures in the phylogenomic analysis of protein domains introduced many mechanistic step types that were later combinatorially spread in catalytic history. The most common mechanistic step types included fundamental building blocks of enzyme chemistry: "Proton transfer," "Bimolecular nucleophilic addition," "Bimolecular nucleophilic substitution," and "Unimolecular elimination by the conjugate base." They were associated with the most ancestral fold structure typical of P-loop containing nucleotide triphosphate hydrolases. Over half of the mechanistic step types were introduced in the evolutionary timeline before the appearance of structures specific to diversified organisms, during a period of architectural diversification. The other half unfolded gradually after organismal diversification and during a

  16. Interactions among the early Escherichia coli divisome proteins revealed by bimolecular fluorescence complementation.

    Science.gov (United States)

    Pazos, Manuel; Natale, Paolo; Margolin, William; Vicente, Miguel

    2013-12-01

    We used bimolecular fluorescence complementation (BiFC) assays to detect protein-protein interactions of all possible pairs of the essential Escherichia coli proto-ring components, FtsZ, FtsA and ZipA, as well as the non-essential FtsZ-associated proteins ZapA and ZapB. We found an unexpected interaction between ZipA and ZapB at potential cell division sites, and when co-overproduced, they induced long narrow constrictions at division sites that were dependent on FtsZ. These assays also uncovered an interaction between ZipA and ZapA that was mediated by FtsZ. BiFC with ZapA and ZapB showed that in addition to their expected interaction at midcell, they also interact at the cell poles. BiFC detected interaction between FtsZ and ZapB at midcell and close to the poles. Results from the remaining pairwise combinations confirmed known interactions between FtsZ and ZipA, and ZapB with itself. © 2013 Society for Applied Microbiology and John Wiley & Sons Ltd.

  17. AFD: an application for bi-molecular interaction using axial frequency distribution.

    Science.gov (United States)

    Raza, Saad; Azam, Syed Sikander

    2018-03-06

    Conformational flexibility and generalized structural features are responsible for specific phenomena existing in biological pathways. With advancements in computational chemistry, novel approaches and new methods are required to compare the dynamic nature of biomolecules, which are crucial not only to address dynamic functional relationships but also to gain detailed insights into the disturbance and positional fluctuation responsible for functional shifts. Keeping this in mind, axial frequency distribution (AFD) has been developed, designed, and implemented. AFD can profoundly represent distribution and density of ligand atom around a particular atom or set of atoms. It enabled us to obtain an explanation of local movements and rotations, which are not significantly highlighted by any other structural and dynamical parameters. AFD can be implemented on biological models representing ligand and protein interactions. It shows a comprehensive view of the binding pattern of ligand by exploring the distribution of atoms relative to the x-y plane of the system. By taking a relative centroid on protein or ligand, molecular interactions like hydrogen bonds, van der Waals, polar or ionic interaction can be analyzed to cater the ligand movement, stabilization or flexibility with respect to the protein. The AFD graph resulted in the residual depiction of bi-molecular interaction in gradient form which can yield specific information depending upon the system of interest.

  18. Study on synthesis, application and mechanism of benzophenone/amine initiator

    International Nuclear Information System (INIS)

    Xiong Wei; Liu Jinshui; Wen Yinjun; Wan Qizhong; Zhou Xianyan; Xiao Hanling; Yang Jianwen

    1999-01-01

    Through Michael addition reaction of trimethylolpropane triacrylate (TMPTA) with diethylamine (DEA), a new kind of tertiary amine derivative was synthesized and its structure was identified by 'H-NMR. When used in combination with benzophenone, this amine presented excellent curing speed and could be a substitute for initiator Darocur R 1173, which is effective but expensive. If so, the cost of UV-curable coatings can descend apparently. The functioning mechanism of benzophenone/amine bimolecular initiator was studied

  19. Bimolecular Complementation to Visualize Filovirus VP40-Host Complexes in Live Mammalian Cells: Toward the Identification of Budding Inhibitors

    Directory of Open Access Journals (Sweden)

    Yuliang Liu

    2011-01-01

    Full Text Available Virus-host interactions play key roles in promoting efficient egress of many RNA viruses, including Ebola virus (EBOV or “e” and Marburg virus (MARV or “m”. Late- (L- domains conserved in viral matrix proteins recruit specific host proteins, such as Tsg101 and Nedd4, to facilitate the budding process. These interactions serve as attractive targets for the development of broad-spectrum budding inhibitors. A major gap still exists in our understanding of the mechanism of filovirus budding due to the difficulty in detecting virus-host complexes and mapping their trafficking patterns in the natural environment of the cell. To address this gap, we used a bimolecular complementation (BiMC approach to detect, localize, and follow the trafficking patterns of eVP40-Tsg101 complexes in live mammalian cells. In addition, we used the BiMC approach along with a VLP budding assay to test small molecule inhibitors identified by in silico screening for their ability to block eVP40 PTAP-mediated interactions with Tsg101 and subsequent budding of eVP40 VLPs. We demonstrated the potential broad spectrum activity of a lead candidate inhibitor by demonstrating its ability to block PTAP-dependent binding of HIV-1 Gag to Tsg101 and subsequent egress of HIV-1 Gag VLPs.

  20. Enhanced bimolecular exchange reaction through programmed coordination of a five-coordinate oxovanadium complex for efficient redox mediation in dye-sensitized solar cells.

    Science.gov (United States)

    Oyaizu, Kenichi; Hayo, Noriko; Sasada, Yoshito; Kato, Fumiaki; Nishide, Hiroyuki

    2013-12-07

    Electrochemical reversibility and fast bimolecular exchange reaction found for VO(salen) gave rise to a highly efficient redox mediation to enhance the photocurrent of a dye-sensitized solar cell, leading to an excellent photovoltaic performance with a conversion efficiency of 5.4%. A heterogeneous electron-transfer rate constant at an electrode (k0) and a second-order rate constant for an electron self-exchange reaction (k(ex)) were proposed as key parameters that dominate the charge transport property, which afforded a novel design concept for the mediators based on their kinetic aspects.

  1. Picosecond real time study of the bimolecular reaction O(3P)+C2H4 and the unimolecular photodissociation of CH3CHO and H2CO

    Science.gov (United States)

    Abou-Zied, Osama K.; McDonald, J. Douglas

    1998-07-01

    The bimolecular reaction of O(3P) with ethylene and the unimolecular photodissociation of acetaldehyde and formaldehyde have been studied using a picosecond pump/probe technique. The bimolecular reaction was initiated in a van der Waals dimer precursor, C2H4ṡNO2, and the evolution of the vinoxy radical product monitored by laser-induced fluorescence. The NO2 constituent of the complex was photodissociated at 266 nm. The triplet oxygen atom then attacks a carbon atom of C2H4 to form a triplet diradical (CH2CH2O) which subsequently dissociates to vinoxy (CH2CHO) and H. The rise time of vinoxy radical production was measured to be 217 (+75-25) ps. RRKM theory was applied and a late high exit barrier was invoked in order to fit the measured rise time. The structure and binding energy of the van der Waals complex have been modeled using Lennard-Jones type potentials and the results were compared with other systems. The unimolecular side of the potential energy surfaces of this reaction has been investigated by photodissociating acetaldehyde at the same pump energy of 266 nm. The resulting photoproducts, acetyl radical (CH3CO) and formyl radical (HCO), have been monitored by resonance enhanced multiphoton ionization (REMPI) combined with a time-of-flight mass spectrometer. The similarity in the measured evolution times of both radicals indicates the same photodissociation pathway of the parent molecule. The photodissociation rate of acetaldehyde is estimated from RRKM theory to be very fast (3×1012s-1). The T1←S1 intersystem crossing (ISC) rate is found to be the rate determining step to photodissociation and increases with energy. The REMPI mechanism for the production of CH3CO+ is proposed to be the same as that of HCO+(2+1). The HCO product from the photodissociation of formaldehyde at 266 nm reveals a faster T1←S1 ISC rate than in acetaldehyde.

  2. Bimolecular Excited-State Electron Transfer with Surprisingly Long-Lived Radical Ions

    KAUST Repository

    Alsam, Amani Abdu; Aly, Shawkat Mohammede; Usman, Anwar; Parida, Manas R.; Del Gobbo, Silvano; Alarousu, Erkki; Mohammed, Omar F.

    2015-01-01

    We explored the excited-state interactions of bimolecular, non-covalent systems consisting of cationic poly[(9,9-di(3,3’-N,N’-trimethyl-ammonium) propyl fluorenyl-2,7-diyl)-alt-co-(9,9-dioctyl-fluorenyl-2,7-diyl)] diiodide salt (PFN) and 1,4-dicyanobenzene (DCB) using steady-state and time-resolved techniques, including femto- and nanosecond transient absorption and femtosecond infrared spectroscopies with broadband capabilities. The experimental results demonstrated that photo-induced electron transfer from PFN to DCB occurs on the picosecond time scale, leading to the formation of PFN+• and DCB-• radical ions. Interestingly, real-time observations of the vibrational marker modes on the acceptor side provided direct evidence and insight into the electron transfer process indirectly inferred from UV-Vis experiments. The band narrowing on the picosecond time scale observed on the antisymmetric C-N stretching vibration of the DCB radical anion provides clear experimental evidence that a substantial part of the excess energy is channeled into vibrational modes of the electron transfer product and that the geminate ion pairs dissociate. More importantly, our nanosecond time-resolved data indicate that the charge-separated state is very long lived ( 30 ns) due to the dissociation of the contact radical ion pair into free ions. Finally, the fast electron transfer and slow charge recombination anticipate the current donor−acceptor system with potential applications in organic solar cells.

  3. Bimolecular Excited-State Electron Transfer with Surprisingly Long-Lived Radical Ions

    KAUST Repository

    Alsam, Amani Abdu

    2015-09-02

    We explored the excited-state interactions of bimolecular, non-covalent systems consisting of cationic poly[(9,9-di(3,3’-N,N’-trimethyl-ammonium) propyl fluorenyl-2,7-diyl)-alt-co-(9,9-dioctyl-fluorenyl-2,7-diyl)] diiodide salt (PFN) and 1,4-dicyanobenzene (DCB) using steady-state and time-resolved techniques, including femto- and nanosecond transient absorption and femtosecond infrared spectroscopies with broadband capabilities. The experimental results demonstrated that photo-induced electron transfer from PFN to DCB occurs on the picosecond time scale, leading to the formation of PFN+• and DCB-• radical ions. Interestingly, real-time observations of the vibrational marker modes on the acceptor side provided direct evidence and insight into the electron transfer process indirectly inferred from UV-Vis experiments. The band narrowing on the picosecond time scale observed on the antisymmetric C-N stretching vibration of the DCB radical anion provides clear experimental evidence that a substantial part of the excess energy is channeled into vibrational modes of the electron transfer product and that the geminate ion pairs dissociate. More importantly, our nanosecond time-resolved data indicate that the charge-separated state is very long lived ( 30 ns) due to the dissociation of the contact radical ion pair into free ions. Finally, the fast electron transfer and slow charge recombination anticipate the current donor−acceptor system with potential applications in organic solar cells.

  4. Bimolecular Fluorescence Complementation of Alpha-synuclein Demonstrates its Oligomerization with Dopaminergic Phenotype in Mice

    Directory of Open Access Journals (Sweden)

    Waijiao Cai

    2018-03-01

    Full Text Available Alpha-synuclein (αSyn is encoded by the first causal gene identified in Parkinson's disease (PD and is the main component of Lewy bodies, a pathological hallmark of PD. aSyn-based animal models have contributed to our understanding of PD pathophysiology and to the development of therapeutics. Overexpression of human wildtype αSyn by viral vectors in rodents recapitulates the loss of dopaminergic neurons from the substantia nigra, another defining pathological feature of the disease. The development of a rat model exhibiting bimolecular fluorescence complementation (BiFC of αSyn by recombinant adeno-associated virus facilitates detection of the toxic αSyn oligomers species. We report here neurochemical, neuropathological and behavioral characterization of BiFC of αSyn in mice. Overexpression and oligomerization of αSyn through BiFC is detected by conjugated fluorescence. Reduced striatal dopamine and loss of nigral dopaminergic neurons are accompanied neuroinflammation and abnormal motor activities. Our mouse model may provide a valuable tool to study the role of αSyn in PD and to explore therapeutic approaches. Keywords: Parkinson's disease, Alpha-synuclein, Mouse model, Oligomers, Neuroinflammation

  5. Exciplex formation in bimolecular photoinduced electron-transfer investigated by ultrafast time-resolved infrared spectroscopy.

    Science.gov (United States)

    Koch, Marius; Letrun, Romain; Vauthey, Eric

    2014-03-12

    The dynamics of bimolecular photoinduced electron-transfer reactions has been investigated with three donor/acceptor (D/A) pairs in tetrahydrofuran (THF) and acetonitrile (ACN) using a combination of ultrafast spectroscopic techniques, including time-resolved infrared absorption. For the D/A pairs with the highest driving force of electron transfer, all transient spectroscopic features can be unambiguously assigned to the excited reactant and the ionic products. For the pair with the lowest driving force, three additional transient infrared bands, more intense in THF than in ACN, with a time dependence that differs from those of the other bands are observed. From their frequency and solvent dependence, these bands can be assigned to an exciplex. Moreover, polarization-resolved measurements point to a relatively well-defined mutual orientation of the constituents and to a slower reorientational time compared to those of the individual reactants. Thanks to the minimal overlap of the infrared signature of all transient species in THF, a detailed reaction scheme including the relevant kinetic and thermodynamic parameters could be deduced for this pair. This analysis reveals that the formation and recombination of the ion pair occur almost exclusively via the exciplex.

  6. Title: Elucidation of Environmental Fate of Artificial Sweeteners (Aspartame, Acesulfame K and Saccharin) by Determining Bimolecular Rate Constants with Hydroxyl Radical at Various pH and Temperature Conditions and Possible Reaction By-Products

    Science.gov (United States)

    Teraji, T.; Arakaki, T.; Suzuka, T.

    2012-12-01

    Use of artificial sweeteners in beverages and food has been rapidly increasing because of their non-calorie nature. In Japan, aspartame, acesulfame K and sucralose are among the most widely used artificial sweeteners. Because the artificial sweeteners are not metabolized in human bodies, they are directly excreted into the environment without chemical transformations. We initiated a study to better understand the fate of artificial sweeteners in the marine environment. The hydroxyl radical (OH), the most potent reactive oxygen species, reacts with various compounds and determines the environmental oxidation capacity and the life-time of many compounds. The steady-state OH concentration and the reaction rate constants between the compound and OH are used to estimate the life-time of the compound. In this study, we determine the bimolecular rate constants between aspartame, acefulfame K and saccharin and OH at various pH and temperature conditions using a competition kinetics technique. We use hydrogen peroxide as a photochemical source of OH. Bimolecular rate constant we obtained so far for aspartame was (2.6±1.2)×109 M-1 s-1 at pH = 3.0 and (4.9±2.3)×109 M-1 s-1 at pH = 5.5. Little effect was seen by changing the temperatures between 15 and 40 oC. Activation energy (Ea) was calculated to be -1.0 kJ mol-1 at pH = 3.0, +8.5 kJ mol-1 at pH = 5.5, which could be regarded as zero. We will report bimolecular rate constants at different pHs and temperatures for acesulfame K and saccharin, as well. Possible reaction by-products for aspartame will be also reported. We will further discuss the fate of aspartame in the coastal environment.

  7. Structure-activity correlations for TON, FER and MOR in the hydroisomerization of n-butane

    NARCIS (Netherlands)

    Pieterse, J.A.Z.; Seshan, Kulathuiyer; Lercher, J.A.

    2000-01-01

    n-Butane hydroconversion was studied over (Pt-loaded) molecular sieves with TON, FER, and MOR morphology. The conversion occurs via a complex interplay of mono- and bimolecular bifunctional acid mechanism and monofunctional platinum-catalyzed hydrogenolysis. Hydroisomerization occurs bimolecularly

  8. Unraveling the role of entropy in tuning unimolecular vs . bimolecular reaction rates: The case of olefin polymerization catalyzed by transition metals

    KAUST Repository

    Falivene, Laura

    2018-04-24

    Olefin polymerization catalyzed by Group 4 transition metals is studied here as test case to reveal the entropy effects when bimolecular and unimolecular reactions are computed for processes occurring in solution. Catalytic systems characterized by different ligand frameworks, metal, and growing polymeric chain for which experimental data are available have been selected in order to validate the main approaches to entropy calculation. Applying the “standard” protocol results in a strong disagreement with the experimental results and the methods introducing a direct correction of the translational entropy term based on a single experimental parameter emerge as the most reliable. The general and powerful computational tool achieved in this study can represent a further step towards the “catalyst design” to control and predict the molecular mass of the resulting polymers.

  9. Computational study of hydrogen shifts and ring-opening mechanisms in α-pinene ozonolysis products

    DEFF Research Database (Denmark)

    Kurtén, Theo; Rissanen, Matti P.; Mackeprang, Kasper

    2015-01-01

    , sterically unhindered) H-shifts of all four peroxy radicals formed in the ozonolysis of α-pinene using density functional (ωB97XD) and coupled cluster [CCSD(T)-F12] theory. In contrast to the related but chemically simpler cyclohexene ozonolysis system, none of the calculated H-shifts have rate constants...... products in the α-pinene ozonolysis system, additional ring-opening reaction mechanisms breaking the cyclobutyl ring are therefore needed. We further investigate possible uni- and bimolecular pathways for opening the cyclobutyl ring in the α-pinene ozonolysis system....

  10. Photoinduced bimolecular electron transfer kinetics in small unilamellar vesicles

    International Nuclear Information System (INIS)

    Choudhury, Sharmistha Dutta; Kumbhakar, Manoj; Nath, Sukhendu; Pal, Haridas

    2007-01-01

    Photoinduced electron transfer (ET) from N,N-dimethylaniline to some coumarin derivatives has been studied in small unilamellar vesicles (SUVs) of the phospholipid, DL-α-dimyristoyl-phosphatidylcholine, using steady-state and time-resolved fluorescence quenching, both below and above the phase transition temperature of the vesicles. The primary interest was to examine whether Marcus inversion [H. Sumi and R. A. Marcus, J. Chem. Phys. 84, 4894 (1986)] could be observed for the present ET systems in these organized assemblies. The influence of the topology of SUVs on the photophysical properties of the reactants and consequently on their ET kinetics has also been investigated. Absorption and fluorescence spectral data of the coumarins in SUVs and the variation of their fluorescence decays with temperature indicate that the dyes are localized in the bilayer of the SUVs. Time-resolved area normalized emission spectra analysis, however, reveals that the dyes are distributed in two different microenvironments in the SUVs, which we attribute to the two leaflets of the bilayer, one toward bulk water and the other toward the inner water pool. The microenvironments in the two leaflets are, however, not indicated to be that significantly different. Time-resolved anisotropy decays were biexponential for all the dyes in SUVs, and this has been interpreted in terms of the compound motion model according to which the dye molecules can experience a fast wobbling-in-cone type of motion as well as a slow overall rotating motion of the cone containing the molecule. The expected bimolecular diffusion-controlled rates in SUVs, as estimated by comparing the microviscosities in SUVs (determined from rotational correlation times) and that in acetonitrile solution, are much slower than the observed fluorescence quenching rates, suggesting that reactant diffusion (translational) does not play any role in the quenching kinetics in the present systems. Accordingly, clear inversions are

  11. Switching and sensing spin states of co-porphyrin in bimolecular reactions on Au111 using scanning tunneling microscopy.

    Science.gov (United States)

    Kim, Howon; Chang, Yun Hee; Lee, Soon-Hyeong; Kim, Yong-Hyun; Kahng, Se-Jong

    2013-10-22

    Controlling and sensing spin states of magnetic molecules at the single-molecule level is essential for spintronic molecular device applications. Here, we demonstrate that spin states of Co-porphyrin on Au(111) can be reversibly switched over by binding and unbinding of the NO molecule and can be sensed using scanning tunneling microscopy and spectroscopy (STM and STS). Before NO exposure, Co-porphryin showed a clear zero-bias peak, a signature of Kondo effect in STS, whereas after NO exposures, it formed a molecular complex, NO-Co-porphyrin, that did not show any zero-bias feature, implying that the Kondo effect was switched off by binding of NO. The Kondo effect could be switched back on by unbinding of NO through single-molecule manipulation or thermal desorption. Our density functional theory calculation results explain the observations with pairing of unpaired spins in dz(2) and ppπ* orbitals of Co-porphyrin and NO, respectively. Our study opens up ways to control molecular spin state and Kondo effect by means of enormous variety of bimolecular binding and unbinding reactions on metallic surfaces.

  12. Bimolecular Rate Constants for FAD-Dependent Glucose Dehydrogenase from Aspergillus terreus and Organic Electron Acceptors.

    Science.gov (United States)

    Tsuruoka, Nozomu; Sadakane, Takuya; Hayashi, Rika; Tsujimura, Seiya

    2017-03-10

    The flavin adenine dinucleotide-dependent glucose dehydrogenase (FAD-GDH) from Aspergillus species require suitable redox mediators to transfer electrons from the enzyme to the electrode surface for the application of bioelectrical devices. Although several mediators for FAD-GDH are already in use, they are still far from optimum in view of potential, kinetics, sustainability, and cost-effectiveness. Herein, we investigated the efficiency of various phenothiazines and quinones in the electrochemical oxidation of FAD-GDH from Aspergillus terreus . At pH 7.0, the logarithm of the bimolecular oxidation rate constants appeared to depend on the redox potentials of all the mediators tested. Notably, the rate constant of each molecule for FAD-GDH was approximately 2.5 orders of magnitude higher than that for glucose oxidase from Aspergillus sp. The results suggest that the electron transfer kinetics is mainly determined by the formal potential of the mediator, the driving force of electron transfer, and the electron transfer distance between the redox active site of the mediator and the FAD, affected by the steric or chemical interactions. Higher k ₂ values were found for ortho-quinones than for para-quinones in the reactions with FAD-GDH and glucose oxidase, which was likely due to less steric hindrance in the active site in the case of the ortho-quinones.

  13. Bimolecular Rate Constants for FAD-Dependent Glucose Dehydrogenase from Aspergillus terreus and Organic Electron Acceptors

    Directory of Open Access Journals (Sweden)

    Nozomu Tsuruoka

    2017-03-01

    Full Text Available The flavin adenine dinucleotide-dependent glucose dehydrogenase (FAD-GDH from Aspergillus species require suitable redox mediators to transfer electrons from the enzyme to the electrode surface for the application of bioelectrical devices. Although several mediators for FAD-GDH are already in use, they are still far from optimum in view of potential, kinetics, sustainability, and cost-effectiveness. Herein, we investigated the efficiency of various phenothiazines and quinones in the electrochemical oxidation of FAD-GDH from Aspergillus terreus. At pH 7.0, the logarithm of the bimolecular oxidation rate constants appeared to depend on the redox potentials of all the mediators tested. Notably, the rate constant of each molecule for FAD-GDH was approximately 2.5 orders of magnitude higher than that for glucose oxidase from Aspergillus sp. The results suggest that the electron transfer kinetics is mainly determined by the formal potential of the mediator, the driving force of electron transfer, and the electron transfer distance between the redox active site of the mediator and the FAD, affected by the steric or chemical interactions. Higher k2 values were found for ortho-quinones than for para-quinones in the reactions with FAD-GDH and glucose oxidase, which was likely due to less steric hindrance in the active site in the case of the ortho-quinones.

  14. In vitro and in vivo mapping of the Prunus necrotic ringspot virus coat protein C-terminal dimerization domain by bimolecular fluorescence complementation.

    Science.gov (United States)

    Aparicio, Frederic; Sánchez-Navarro, Jesús A; Pallás, Vicente

    2006-06-01

    Interactions between viral proteins are critical for virus viability. Bimolecular fluorescent complementation (BiFC) technique determines protein interactions in real-time under almost normal physiological conditions. The coat protein (CP) of Prunus necrotic ringspot virus is required for multiple functions in its replication cycle. In this study, the region involved in CP dimerization has been mapped by BiFC in both bacteria and plant tissue. Full-length and C-terminal deleted forms of the CP gene were fused in-frame to the N- and C-terminal fragments of the yellow fluorescent protein. The BiFC analysis showed that a domain located between residues 9 and 27 from the C-end plays a critical role in dimerization. The importance of this C-terminal region in dimer formation and the applicability of the BiFC technique to analyse viral protein interactions are discussed.

  15. Bimodal Exciplex Formation in Bimolecular Photoinduced Electron Transfer Revealed by Ultrafast Time-Resolved Infrared Absorption.

    Science.gov (United States)

    Koch, Marius; Licari, Giuseppe; Vauthey, Eric

    2015-09-03

    The dynamics of a moderately exergonic photoinduced charge separation has been investigated by ultrafast time-resolved infrared absorption with the dimethylanthracene/phthalonitrile donor/acceptor pair in solvents covering a broad range of polarity. A distinct spectral signature of an exciplex could be identified in the -C≡N stretching region. On the basis of quantum chemistry calculations, the 4-5 times larger width of this band compared to those of the ions and of the locally excited donor bands is explained by a dynamic distribution of exciplex geometry with different mutual orientations and distances of the constituents and, thus, with varying charge-transfer character. Although spectrally similar, two types of exciplexes could be distinguished by their dynamics: short-lived, "tight", exciplexes generated upon static quenching and longer-lived, "loose", exciplexes formed upon dynamic quenching in parallel with ion pairs. Tight exciplexes were observed in all solvents, except in the least polar diethyl ether where quenching is slower than diffusion. The product distribution of the dynamic quenching depends strongly on the solvent polarity: whereas no significant loose exciplex population could be detected in acetonitrile, both exciplex and ion pair are generated in less polar solvents, with the relative population of exciplex increasing with decreasing solvent polarity. These results are compared with those reported previously with donor/acceptor pairs in different driving force regimes to obtain a comprehensive picture of the role of the exciplexes in bimolecular photoinduced charge separation.

  16. Phosphorelay of non-orthodox two component systems functions through a bi-molecular mechanism in vivo

    DEFF Research Database (Denmark)

    Jovanovic, Goran; Sheng, Xia; Ale, Angelique

    2015-01-01

    the functional relevance of the dimerization of a non-orthodox or hybrid histidine kinase along which the phosphorelay takes place has been a subject of debate. We use a combination of molecular and genetic approaches, coupled to mathematical and statistical modelling, to demonstrate that the different possible...... intra- and inter-molecular mechanisms of phosphotransfer are formally non-identifiable in Escherichia coli expressing the ArcB non-orthodox histidine kinase used in anoxic redox control. In order to resolve this issue we further analyse the mathematical model in order to identify discriminatory...

  17. Formation of Bimolecular Membranes from Lipid Monolayers and a Study of Their Electrical Properties

    Science.gov (United States)

    Montal, M.; Mueller, P.

    1972-01-01

    Bimolecular membranes are formed from two lipid monolayers at an air-water interface by the apposition of their hydrocarbon chains when an aperture in a Teflon partition separating two aqueous phases is lowered through the interface. Formation of the membrane is monitored by an increase of the electrical capacity, as measured with a voltage clamp. Electrical resistance of the unmodified membrane is analogous to that of conventional planar bilayers (black lipid membranes) prepared in the presence of a hydrocarbon solvent, i.e., 106-108 ohm cm2; the resistance can be lowered to values of 103 ohm cm2 by gramicidin, an antibiotic that modifies the conductance only when the membranes are of biomolecular thickness. In contrast to the resistance, there is a significant difference between the capacity of bilayers made from mono-layers and that of hydrocarbon-containing bilayers made by phase transition; the average values are 0.9 and 0.45 μF cm-2, respectively. The value of 0.9 μF cm-2 approximates that of biological membranes. Assuming a dielectric constant of 2.1 for the hydrocarbon region, the dielectric thickness, as calculated from a capacity of 0.9 μF cm-2, is 22 Å. This value is 6-10 Å smaller than the actual thickness of the hydrocarbon region of bilayers and cell membranes, as determined by x-ray diffraction. The difference may be due to a limited penetration of water into the hydrocarbon region near the ester groups that would lower the electrical resistance of this region and reduce the dielectric thickness. Asymmetric membranes have been formed by adjoining two lipid monolayers of different chemical composition. Images PMID:4509315

  18. Detection of Heteromers Formed by Cannabinoid CB1, Dopamine D2, and Adenosine A2A G-Protein-Coupled Receptors by Combining Bimolecular Fluorescence Complementation and Bioluminescence Energy Transfer

    Science.gov (United States)

    Navarro, Gemma; Carriba, Paulina; Gandí, Jorge; Ciruela, Francisco; Casadó, Vicent; Cortés, Antoni; Mallol, Josefa; Canela, Enric I.; Lluis, Carmen; Franco, Rafael

    2008-01-01

    Functional interactions in signaling occur between dopamine D2 (D2R) and cannabinoid CB1 (CB1R) receptors, between CB1R and adenosine A2A (A2AR) receptors, and between D2R and A2AR. Furthermore, direct molecular interactions have been reported for the pairs CB1R-D2R, A2AR-D2R, and CB1R-A2AR. Here a combination of bimolecular fluorescence complementation and bioluminescence energy transfer techniques was used to identify the occurrence of D2R-CB1R-A2AR hetero-oligomers in living cells. PMID:18956124

  19. Detection of Heteromers Formed by Cannabinoid CB1, Dopamine D2, and Adenosine A2A G-Protein-Coupled Receptors by Combining Bimolecular Fluorescence Complementation and Bioluminescence Energy Transfer

    Directory of Open Access Journals (Sweden)

    Gemma Navarro

    2008-01-01

    Full Text Available Functional interactions in signaling occur between dopamine D2 (D2R and cannabinoid CB1 (CB1R receptors, between CB1R and adenosine A2A (A2AR receptors, and between D2R and A2AR. Furthermore, direct molecular interactions have been reported for the pairs CB1R-D2R, A2AR-D2R, and CB1R-A2AR. Here a combination of bimolecular fluorescence complementation and bioluminescence energy transfer techniques was used to identify the occurrence of D2R-CB1R-A2AR hetero-oligomers in living cells.

  20. An approximate method for calculating composition of the non-equilibrium explosion products of hydrocarbons and oxygen

    International Nuclear Information System (INIS)

    Shargatov, V A; Gubin, S A; Okunev, D Yu

    2016-01-01

    We develop a method for calculating the changes in composition of the explosion products in the case where the complete chemical equilibrium is absent but the bimolecular reactions are in quasi-equilibrium with the exception bimolecular reactions with one of the components of the mixture. We investigate the possibility of using the method of 'quasiequilibrium' for mixtures of hydrocarbons and oxygen. The method is based on the assumption of the existence of the partial chemical equilibrium in the explosion products. Without significant loss of accuracy to the solution of stiff differential equations detailed kinetic mechanism can be replaced by one or two differential equation and a system of algebraic equations. This method is always consistent with the detailed mechanism and can be used separately or in conjunction with the solution of a stiff system for chemically non-equilibrium mixtures replacing it when bimolecular reactions are near to equilibrium. (paper)

  1. Bimolecular interaction of argpyrimidine (a Maillard reaction product) in in vitro non-enzymatic protein glycation model and its potential role as an antiglycating agent.

    Science.gov (United States)

    Bhattacherjee, Abhishek; Dhara, Kaliprasanna; Chakraborti, Abhay Sankar

    2017-09-01

    Non- enzymatic glycation, also known as Maillard reaction, is one of the most important and investigated reactions in biochemistry. Maillard reaction products (MRPs) like protein-derived advanced glycation end products (AGEs) are often referred to cause pathophysiological complications in human systems. On contrary, several MRPs are exogenously used as antioxidant, antimicrobial and flavouring agents. In the preset study, we have shown that argpyrimidine, a well-established AGE, interacts with bovine serum albumin (BSA) and glucose individually in standard BSA-glucose model system and successfully inhibits glycation of the protein. Bimolecular interaction of argpyrimidine with glucose or BSA has been studied independently. Chromatographic purification, different spectroscopic studies and molecular modeling have been used to evaluate the nature and pattern of interactions. Binding of argpyrimidine with BSA prevents incorporation of glucose inside the native protein. Argpyrimidine can also directly entrap glucose. Both these interactions may be associated with the antiglycation potential of argpyrimidine, indicating a beneficial function of an AGE. Copyright © 2017 Elsevier B.V. All rights reserved.

  2. Isotopic study on mechanism for skeletal isomerization of n-butane over solid acids

    International Nuclear Information System (INIS)

    Suzuki, Tetsuo; Okuhara, Toshio

    2000-01-01

    Reaction mechanism for skeletal isomerization of n-butane over typical strong solid acids were investigated by using 1,4- 13 C 2 -n-butane. We used FI MASS for the analysis of 13 C distribution to get the parent pattern. 13 C-distribution of isobutane formed at 423 K over SO 3 2- /ZrO 2 (SZ) and Cs 2.5 H 0.5 PW 12 O 40 (Cs2.5) were close to binomial distributions, indicating that the isomerization proceeded mainly via a bimolecular mechanism on these catalysts. On the other hand, at 523 K over Cs2.5, the isotopic distribution pattern in isobutane was quite different from the binomial one; the fraction of 13 C 2 -isobutane was much greater than the binomial distribution. This result demonstrates that an intramolecular (monomolecular) rearrangement became significant at 523 K over Cs2.5. The contribution of monomolecular pathway was higher on Cs2.5 than on SZ. We presumed that the contribution of mechanism is related to the acidic property and the dehydrogenation ability of the catalyst. (S.Y.)

  3. 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.

  4. Mechanism of alternating copolymerization of methyl methacrylate with styrene in the presence of diethylaluminum chloride

    International Nuclear Information System (INIS)

    Zubov, V.P.; Lachinov, M.B.; Ignatova, E.V.; Georgiev, G.S.; Golubev, V.B.; Kabanov, V.A.

    1982-01-01

    A kinetic study of the propagation mechanism of the alternating copolymerization of styrene (St) with methyl methacrylate (MMA) in the presence of a complexing agent (diethylaluminum chloride, DEAC) in bulk and in tetrachloroethylene solutions at a molar ratio DEAC/MMA = 0.5 has been carried out. It has been shown that the copolymerization is a chain radical process characterized by a short active-center lifetime, bimolecular termination, and high rate of chain transfer to the complexed MMA. A kinetic scheme has been proposed for the propagation mechanism of alternating copolymerization in the presence of a complexing agent not requiring independent measurements of the equilibrium constant of complexation. It has been found that spontaneous and uv-initiated copolymerizations in the system have different mechanisms of initiation and a common mechanism of propagation. The propagation proceeds by addition of single monomers as well as donor-acceptor complexes of the comonomers to the propagation radicals, with the first mechanism being predominant. Inclusion of the monomers in the complex leads to an increase of the St reactivity and to a decrease of the MMA reactivity in propagation to the corresponding macroradicals in comparison with the reactivity of the free monomers. A number of kinetic and statistical parameters of the propagation reaction have been calculated

  5. Theoretical study of the oxidation mechanisms of naphthalene initiated by hydroxyl radicals: the OH-addition pathway.

    Science.gov (United States)

    Shiroudi, Abolfazl; Deleuze, Michael S; Canneaux, Sébastien

    2014-07-03

    The oxidation mechanisms of naphthalene by OH radicals under inert (He) conditions have been studied using density functional theory along with various exchange-correlation functionals. Comparison has been made with benchmark CBS-QB3 theoretical results. Kinetic rate constants were correspondingly estimated by means of transition state theory and statistical Rice-Ramsperger-Kassel-Marcus (RRKM) theory. Comparison with experiment confirms that, on the OH-addition reaction pathway leading to 1-naphthol, the first bimolecular reaction step has an effective negative activation energy around -1.5 kcal mol(-1), whereas this step is characterized by an activation energy around 1 kcal mol(-1) on the OH-addition reaction pathway leading to 2-naphthol. Effective rate constants have been calculated according to a steady state analysis upon a two-step model reaction mechanism. In line with experiment, the correspondingly obtained branching ratios indicate that, at temperatures lower than 410 K, the most abundant product resulting from the oxidation of naphthalene by OH radicals must be 1-naphthol. The regioselectivity of the OH(•)-addition onto naphthalene decreases with increasing temperatures and decreasing pressures. Because of slightly positive or even negative activation energies, the RRKM calculations demonstrate that the transition state approximation breaks down at ambient pressure (1 bar) for the first bimolecular reaction steps. Overwhelmingly high pressures, larger than 10(5) bar, would be required for restoring to some extent (within ∼5% accuracy) the validity of this approximation for all the reaction channels that are involved in the OH-addition pathway. Analysis of the computed structures, bond orders, and free energy profiles demonstrate that all reaction steps involved in the oxidation of naphthalene by OH radicals satisfy Leffler-Hammond's principle. Nucleus independent chemical shift indices and natural bond orbital analysis also show that the computed

  6. Live cell imaging of interactions between replicase and capsid protein of Brome mosaic virus using Bimolecular Fluorescence Complementation: implications for replication and genome packaging.

    Science.gov (United States)

    Chaturvedi, Sonali; Rao, A L N

    2014-09-01

    In Brome mosaic virus, it was hypothesized that a physical interaction between viral replicase and capsid protein (CP) is obligatory to confer genome packaging specificity. Here we tested this hypothesis by employing Bimolecular Fluorescent Complementation (BiFC) as a tool for evaluating protein-protein interactions in living cells. The efficacy of BiFC was validated by a known interaction between replicase protein 1a (p1a) and protein 2a (p2a) at the endoplasmic reticulum (ER) site of viral replication. Additionally, co-expression in planta of a bona fide pair of interacting protein partners of p1a and p2a had resulted in the assembly of a functional replicase. Subsequent BiFC assays in conjunction with mCherry labeled ER as a fluorescent cellular marker revealed that CP physically interacts with p2a, but not p1a, and this CP:p2a interaction occurs at the cytoplasmic phase of the ER. The significance of the CP:p2a interaction in BMV replication and genome packaging is discussed. Copyright © 2014 Elsevier Inc. All rights reserved.

  7. Kinetics and mechanism of hydrolysis of benzimidazolylcarbamates

    OpenAIRE

    Norberto, F. P.; Santos, S. P.; Iley, J.; Silva, D. B.; Corte Real, M.

    2007-01-01

    Synthesis of new 2-aminobenzimidazole-1-carbamates was accomplished by carbamoylation of 2-aminobenzimidazole using different substituted phenyl chloroformates. The aqueous hydrolysis of the new compounds was examined in the pH range 1-13 at 25 ºC. The evaluated kinetic parameters led to the conclusion that up to pH 4 reaction proceeds by a bimolecular attack of water to the N-protonated substrate. This is the first time this behavior is described for carbamates, and can be ascribed to the hi...

  8. Modified reaction mechanism of aerated n-dodecane liquid flowing over heated metal tubes

    Science.gov (United States)

    Reddy, K. T.; Cernansky, N. P.; Cohen, R. S.

    1988-01-01

    The degradation mechanism of the n-dodecane was studied using a modified jet fuel thermal oxidation tester containing a sample withdrawal system as a reaction vessel. The reaction products were identified using gas chromatography and mass spectorometry. The soluble products were found to consist mainly of C5-C10 n-alkanes and 1-alkenes, C7-C10 aldehydes, tetrahydrofuran derivatives, dodecanol and dodecanone isomers, dodecyl hydroperoxide (ROOH) decomposition products, and C24 alkane isomers. The data from the experiments agreed with those of Hazlett et al. (1977). It was found that alkyl peroxide radical reactions dominate in the autooxidation temperature regime (at T not above 300 C); the dominant path is for the alkyl peroxyl radical to react bimolecularly with fuel to yield primarily alkyl hydroperoxides. The alkyl peroxide radical also undergoes self-termination and unimolecular isomerization and decomposition reactions, to yield smaller amounts of C12 alcohol plus ketone products and tetrahydrofuran derivatives, respectively.

  9. Polymer:Nonfullerene Bulk Heterojunction Solar Cells with Exceptionally Low Recombination Rates

    KAUST Repository

    Gasparini, Nicola; Salvador, Michael; Heumueller, Thomas; Richter, Moses; Classen, Andrej; Shrestha, Shreetu; Matt, Gebhard J.; Holliday, Sarah; Strohm, Sebastian; Egelhaaf, Hans-Joachim; Wadsworth, Andrew; Baran, Derya; McCulloch, Iain; Brabec, Christoph J.

    2017-01-01

    Organic semiconductors are in general known to have an inherently lower charge carrier mobility compared to their inorganic counterparts. Bimolecular recombination of holes and electrons is an important loss mechanism and can often be described by the Langevin recombination model. Here, the device physics of bulk heterojunction solar cells based on a nonfullerene acceptor (IDTBR) in combination with poly(3-hexylthiophene) (P3HT) are elucidated, showing an unprecedentedly low bimolecular recombination rate. The high fill factor observed (above 65%) is attributed to non-Langevin behavior with a Langevin prefactor (β/βL) of 1.9 × 10−4. The absence of parasitic recombination and high charge carrier lifetimes in P3HT:IDTBR solar cells inform an almost ideal bimolecular recombination behavior. This exceptional recombination behavior is explored to fabricate devices with layer thicknesses up to 450 nm without significant performance losses. The determination of the photoexcited carrier mobility by time-of-flight measurements reveals a long-lived and nonthermalized carrier transport as the origin for the exceptional transport physics. The crystalline microstructure arrangement of both components is suggested to be decisive for this slow recombination dynamics. Further, the thickness-independent power conversion efficiency is of utmost technological relevance for upscaling production and reiterates the importance of understanding material design in the context of low bimolecular recombination.

  10. Polymer:Nonfullerene Bulk Heterojunction Solar Cells with Exceptionally Low Recombination Rates

    KAUST Repository

    Gasparini, Nicola

    2017-09-01

    Organic semiconductors are in general known to have an inherently lower charge carrier mobility compared to their inorganic counterparts. Bimolecular recombination of holes and electrons is an important loss mechanism and can often be described by the Langevin recombination model. Here, the device physics of bulk heterojunction solar cells based on a nonfullerene acceptor (IDTBR) in combination with poly(3-hexylthiophene) (P3HT) are elucidated, showing an unprecedentedly low bimolecular recombination rate. The high fill factor observed (above 65%) is attributed to non-Langevin behavior with a Langevin prefactor (β/βL) of 1.9 × 10−4. The absence of parasitic recombination and high charge carrier lifetimes in P3HT:IDTBR solar cells inform an almost ideal bimolecular recombination behavior. This exceptional recombination behavior is explored to fabricate devices with layer thicknesses up to 450 nm without significant performance losses. The determination of the photoexcited carrier mobility by time-of-flight measurements reveals a long-lived and nonthermalized carrier transport as the origin for the exceptional transport physics. The crystalline microstructure arrangement of both components is suggested to be decisive for this slow recombination dynamics. Further, the thickness-independent power conversion efficiency is of utmost technological relevance for upscaling production and reiterates the importance of understanding material design in the context of low bimolecular recombination.

  11. Reformulation and solution of the master equation for multiple-well chemical reactions.

    Science.gov (United States)

    Georgievskii, Yuri; Miller, James A; Burke, Michael P; Klippenstein, Stephen J

    2013-11-21

    We consider an alternative formulation of the master equation for complex-forming chemical reactions with multiple wells and bimolecular products. Within this formulation the dynamical phase space consists of only the microscopic populations of the various isomers making up the reactive complex, while the bimolecular reactants and products are treated equally as sources and sinks. This reformulation yields compact expressions for the phenomenological rate coefficients describing all chemical processes, i.e., internal isomerization reactions, bimolecular-to-bimolecular reactions, isomer-to-bimolecular reactions, and bimolecular-to-isomer reactions. The applicability of the detailed balance condition is discussed and confirmed. We also consider the situation where some of the chemical eigenvalues approach the energy relaxation time scale and show how to modify the phenomenological rate coefficients so that they retain their validity.

  12. A mathematical analysis of Prx2-STAT3 disulfide exchange rate constants for a bimolecular reaction mechanism.

    Science.gov (United States)

    Langford, Troy F; Deen, William M; Sikes, Hadley D

    2018-03-22

    Appreciation of peroxiredoxins as the major regulators of H 2 O 2 concentrations in human cells has led to a new understanding of redox signaling. In addition to their status as the primary reducers of H 2 O 2 to water, the oxidized peroxiredoxin byproduct of this reaction has recently been shown capable of participation in H 2 O 2 -mediated signaling pathways through disulfide exchange reactions with the transcription factor STAT3. The dynamics of peroxidase-transcription factor disulfide exchange reactions have not yet been considered in detail with respect to how these reactions fit into the larger network of competing reactions in human cells. In this study, we used a kinetic model of oxidation and reduction reactions related to H 2 O 2 metabolism in the cytosol of human cells to study the dynamics of peroxiredoxin-2 mediated oxidation of the redox-regulated transcription factor STAT3. In combination with previously reported experimental data, the model was used to estimate the rate coefficient of a biomolecular reaction between Prx2 and STAT3 for two sets of assumptions that constitute lower and upper bound cases. Using these estimates, we calculated the relative rates of the reaction of oxidized peroxiredoxin-2 and STAT3 and other competing reactions in the cytosol. These calculations revealed that peroxiredoxin-2-mediated oxidation of STAT3 likely occurs at a much slower rate than competing reactions in the cytosol. This analysis suggests the existence of more complex mechanisms, potentially involving currently unknown protein-protein recognition partners, which facilitate disulfide exchange reactions between peroxiredoxin-2 and STAT3. Copyright © 2018 Elsevier Inc. All rights reserved.

  13. Live cell imaging of interactions between replicase and capsid protein of Brome mosaic virus using Bimolecular Fluorescence Complementation: Implications for replication and genome packaging

    International Nuclear Information System (INIS)

    Chaturvedi, Sonali; Rao, A.L.N.

    2014-01-01

    In Brome mosaic virus, it was hypothesized that a physical interaction between viral replicase and capsid protein (CP) is obligatory to confer genome packaging specificity. Here we tested this hypothesis by employing Bimolecular Fluorescent Complementation (BiFC) as a tool for evaluating protein–protein interactions in living cells. The efficacy of BiFC was validated by a known interaction between replicase protein 1a (p1a) and protein 2a (p2a) at the endoplasmic reticulum (ER) site of viral replication. Additionally, co-expression in planta of a bona fide pair of interacting protein partners of p1a and p2a had resulted in the assembly of a functional replicase. Subsequent BiFC assays in conjunction with mCherry labeled ER as a fluorescent cellular marker revealed that CP physically interacts with p2a, but not p1a, and this CP:p2a interaction occurs at the cytoplasmic phase of the ER. The significance of the CP:p2a interaction in BMV replication and genome packaging is discussed. - Highlights: • YFP fusion proteins of BMV p1a and p2a are biologically active. • Self-interaction was observed for p1a, p2a and CP. • CP interacts with p2a but not p1a. • Majority of reconstituted YFP resulting from bona fide fusion protein partners localized on ER

  14. Live cell imaging of interactions between replicase and capsid protein of Brome mosaic virus using Bimolecular Fluorescence Complementation: Implications for replication and genome packaging

    Energy Technology Data Exchange (ETDEWEB)

    Chaturvedi, Sonali; Rao, A.L.N., E-mail: arao@ucr.edu

    2014-09-15

    In Brome mosaic virus, it was hypothesized that a physical interaction between viral replicase and capsid protein (CP) is obligatory to confer genome packaging specificity. Here we tested this hypothesis by employing Bimolecular Fluorescent Complementation (BiFC) as a tool for evaluating protein–protein interactions in living cells. The efficacy of BiFC was validated by a known interaction between replicase protein 1a (p1a) and protein 2a (p2a) at the endoplasmic reticulum (ER) site of viral replication. Additionally, co-expression in planta of a bona fide pair of interacting protein partners of p1a and p2a had resulted in the assembly of a functional replicase. Subsequent BiFC assays in conjunction with mCherry labeled ER as a fluorescent cellular marker revealed that CP physically interacts with p2a, but not p1a, and this CP:p2a interaction occurs at the cytoplasmic phase of the ER. The significance of the CP:p2a interaction in BMV replication and genome packaging is discussed. - Highlights: • YFP fusion proteins of BMV p1a and p2a are biologically active. • Self-interaction was observed for p1a, p2a and CP. • CP interacts with p2a but not p1a. • Majority of reconstituted YFP resulting from bona fide fusion protein partners localized on ER.

  15. Imperfections and phase transformations by mono-N-alkylammonium-uranium glimmers

    International Nuclear Information System (INIS)

    Kammermeier, H.

    1982-01-01

    Uranium glimmers have a layered structure. Bimolecular intermediate layered films of parallel ordered alkyl chains can be produced by exchange of the intermediate layer kations with the mono-n-alkylammonium ions and the succession of soaking with n-alkanols. Phase changes can occur in these films that are accompanied by a change of the layer distance of the solid inorganic basic matrix. N-alkyl ammonium-n-alkanol-intercalcation compounds of uranium glimmers represent systems that can conveniently be examined with X-rays. Thermal phase changes can be performed easily. This paper describes how one can derive conclusions on the reaction mechanism of phase changes in bimolecular alkyl chain films by means of a profile analysis of X-ray reflexes. (orig./HBR) [de

  16. New mechanism for autocatalytic decomposition of H2CO3 in the vapor phase.

    Science.gov (United States)

    Ghoshal, Sourav; Hazra, Montu K

    2014-04-03

    In this article, we present high level ab initio calculations investigating the energetics of a new autocatalytic decomposition mechanism for carbonic acid (H2CO3) in the vapor phase. The calculation have been performed at the MP2 level of theory in conjunction with aug-cc-pVDZ, aug-cc-pVTZ, and 6-311++G(3df,3pd) basis sets as well as at the CCSD(T)/aug-cc-pVTZ level. The present study suggests that this new decomposition mechanism is effectively a near-barrierless process at room temperature and makes vapor phase of H2CO3 unstable even in the absence of water molecules. Our calculation at the MP2/aug-cc-pVTZ level predicts that the effective barrier, defined as the difference between the zero-point vibrational energy (ZPE) corrected energy of the transition state and the total energy of the isolated starting reactants in terms of bimolecular encounters, is nearly zero for the autocatalytic decomposition mechanism. The results at the CCSD(T)/aug-cc-pVTZ level of calculations suggest that the effective barrier, as defined above, is sensitive to some extent to the levels of calculations used, nevertheless, we find that the effective barrier height predicted at the CCSD(T)/aug-cc-pVTZ level is very small or in other words the autocatalytic decomposition mechanism presented in this work is a near-barrierless process as mentioned above. Thus, we suggest that this new autocatalytic decomposition mechanism has to be considered as the primary mechanism for the decomposition of carbonic acid, especially at its source, where the vapor phase concentration of H2CO3 molecules reaches its highest levels.

  17. Treatment of statin compounds by advanced oxidation processes: Kinetic considerations and destruction mechanisms

    Science.gov (United States)

    Razavi, Behnaz; Song, Weihua; Santoke, Hanoz; Cooper, William J.

    2011-03-01

    This study examined the use of advanced oxidation/reduction processes (AO/RPs) for the destruction of cholesterol lowering statin pharmaceuticals. AO/RPs which utilize the oxidizing hydroxyl radical ( rad OH) and reducing aqueous electron (e -aq), to degrade chemical contaminants are alternatives to traditional water treatment methods, and are alternatives as water reuse becomes more generally implemented. Four major statin pharmaceuticals, fluvastatin, lovastatin, pravastatin and simvastatin, were studied, and the absolute bimolecular reaction rate constants with rad OH determined, (6.96±0.16)×10 9, (2.92±0.06)×10 9, (4.16±0.13)×10 9, and (3.13±0.15)×10 9 M -1 s -1, and for e -aq (2.31±0.06)×10 9, (0.45±0.01)×10 9, (1.26±0.01)×10 9, and (0.69±0.02)×10 9 M -1 s -1, respectively. To provide additional information on the radicals formed upon oxidation, transient spectra were measured and the overall reaction efficiency determined. Radical-based destruction mechanisms for destruction of the statins are proposed based on the LC-MS determination of the stable reaction by-products formed using 137Cs γ-irradiation of statin solutions. Knowing the reaction rates, reaction efficiencies and destruction mechanisms of these compounds is essential for the consideration of the use of advanced oxidation/reduction processes for the destruction of statins in aqueous systems.

  18. Treatment of statin compounds by advanced oxidation processes: Kinetic considerations and destruction mechanisms

    International Nuclear Information System (INIS)

    Razavi, Behnaz; Song Weihua; Santoke, Hanoz; Cooper, William J.

    2011-01-01

    This study examined the use of advanced oxidation/reduction processes (AO/RPs) for the destruction of cholesterol lowering statin pharmaceuticals. AO/RPs which utilize the oxidizing hydroxyl radical ( · OH) and reducing aqueous electron (e - aq ), to degrade chemical contaminants are alternatives to traditional water treatment methods, and are alternatives as water reuse becomes more generally implemented. Four major statin pharmaceuticals, fluvastatin, lovastatin, pravastatin and simvastatin, were studied, and the absolute bimolecular reaction rate constants with · OH determined, (6.96±0.16)x10 9 , (2.92±0.06)x10 9 , (4.16±0.13)x10 9 , and (3.13±0.15)x10 9 M -1 s -1 , and for e - aq (2.31±0.06)x10 9 , (0.45±0.01)x10 9 , (1.26±0.01)x10 9 , and (0.69±0.02)x10 9 M -1 s -1 , respectively. To provide additional information on the radicals formed upon oxidation, transient spectra were measured and the overall reaction efficiency determined. Radical-based destruction mechanisms for destruction of the statins are proposed based on the LC-MS determination of the stable reaction by-products formed using 137 Cs γ-irradiation of statin solutions. Knowing the reaction rates, reaction efficiencies and destruction mechanisms of these compounds is essential for the consideration of the use of advanced oxidation/reduction processes for the destruction of statins in aqueous systems.

  19. The application of the electron beam process in water and wastewater treatment: Fundamental and applied studies

    International Nuclear Information System (INIS)

    Cooper, W.J.; Tobien, T.

    2001-01-01

    We have undertaken a three phase research project that has as the overall goal to better understand the application of the EB process to water, wastewater and sludge treatment. We have conducted studies to examine bimolecular rate constants for several halogenated methanes, several of which are common disinfection by-products when chlorination is practised. The second phase examines the ability to destroy odour causing compounds, we have selected thioanisole as the model compound, in wastewater and sludge treatment. The third phase of our study is to better understand the destruction mechanism and kinetic modelling of the fuel oxygenate, methyl tert-butyl ether, a common ground water contaminant in the US. We report here several new and re-evaluated bimolecular rate constants and the results of large scale EB treatment of water containing the compounds under study. ( author)

  20. Hydrogenation of esters catalyzed by ruthenium PN3-Pincer complexes containing an aminophosphine arm

    KAUST Repository

    Chen, Tao

    2014-08-11

    Hydrogenation of esters under mild conditions was achieved using air-stable ruthenium PN3-pincer complexes containing an aminophosphine arm. High efficiency was achieved even in the presence of water. DFT studies suggest a bimolecular proton shuttle mechanism which allows H2 to be activated by the relatively stable catalyst with a reasonably low transition state barrier. © 2014 American Chemical Society.

  1. On the some reactions of mixed ethers of phosphorus acid with acrylonitrile and methyl iodide

    International Nuclear Information System (INIS)

    Gusev, Yu.K.; Chistokletov, V.N.; Petrov, A.A.

    1977-01-01

    The bimolecular mechanism has been confirmed of the redgrouping stage of Arbuzov's classical reactions for phosphites containing primary and secondary radicals in reactions of acrylonitrile and methyl iodide with some mixed ethers of phosphoric acid. It is suggested that dealcylation of the intermediate products formed on interaction of olefins activated by electron-acceptor groups with phosphites containing primary radicals occurs according to the Ssub(N)2-mechanism, secondary radicals, according to the mixed Ssub(N)2 and Ssub(N)1-mechanism,and radicals capable of forming stable carbonium ions, according to the Ssub(N)1-mechanism

  2. Elucidation of Environmental Fate of Artificial Sweetener, Aspartame by Determining Bimolecular Rate Constants with Hydroxyl Radical at Various pH and Temperature Conditions and Reaction By-Products Presentation type:Poster Section:Ocean Sciences Session:General Contribution Authors:Takashi Teraji (1) Takemitsu Arakaki (2) AGU# 10173629 (1) Graduate School of Engineering and Science, University of the Ryukyus, 1 Senbaru Nishihara-cho, Okinawa, 903-0123, Japan (a4269bj@yahoo.co.jp), (2) Department of Chemistry, Biology and Marine Science, Faculty of Science, University of the Ryukyus, 1 Senbaru Nishihara-cho, Okinawa, 903-0123, Japan (arakakit@sci.u-ryukyu.ac.jp)

    Science.gov (United States)

    Teraji, T.; Arakaki, T.

    2011-12-01

    Use of artificial sweeteners in drinks and food has been rapidly increasing because of their non-calorie nature. In Japan, aspartame, acesulfame K and sucralose are among the most widely used artificial sweeteners. Because the artificial sweeteners are not metabolized in human bodies, they are directly excreted into the environment without chemical transformations. We initiated a study to better understand the fate of artificial sweeteners in the marine environment. In particular, we focused on the fate of aspartame by determining its bimolecular rate constants with hydroxyl radicals at various pH and temperature conditions and reaction by-products. The hydroxyl radical (OH), the most potent reactive oxygen species, reacts with various compounds and determines the environmental oxidation capacity and the life-time of many compounds. The steady-state OH concentration and the reaction rate constants between the compound and OH are used to estimate the life-time of the compound. In this study, we determine the bimolecular rate constants between aspartame and OH at various pH and temperature conditions using a competition kinetics technique. We use hydrogen peroxide as a photochemical source of OH. Bimolecular rate constant we obtained so far was (2.6±1.2)×109 M-1 s-1 at pH = 3.0. Little effect was seen by changing the temperatures between 15 and 40 °C. Activation energy (Ea) was calculated to be -1.0 kJ mol-1 at pH = 3.0, which could be regarded as zero. We will report reaction rate constants at different pHs and reaction by-products which will be analyzed by GC-MS. We will further discuss the fate of aspartame in the coastal environment.

  3. Treatment of statin compounds by advanced oxidation processes: Kinetic considerations and destruction mechanisms

    Energy Technology Data Exchange (ETDEWEB)

    Razavi, Behnaz, E-mail: brazavi@uci.ed [Urban Water Research Center, Department of Civil and Environmental Engineering, University of California, Irvine, Irvine, CA 92697-2175 (United States); Song Weihua, E-mail: wsong@uci.ed [Urban Water Research Center, Department of Civil and Environmental Engineering, University of California, Irvine, Irvine, CA 92697-2175 (United States); Santoke, Hanoz, E-mail: hsantoke@uci.ed [Urban Water Research Center, Department of Civil and Environmental Engineering, University of California, Irvine, Irvine, CA 92697-2175 (United States); Cooper, William J., E-mail: wcooper@uci.ed [Urban Water Research Center, Department of Civil and Environmental Engineering, University of California, Irvine, Irvine, CA 92697-2175 (United States)

    2011-03-15

    This study examined the use of advanced oxidation/reduction processes (AO/RPs) for the destruction of cholesterol lowering statin pharmaceuticals. AO/RPs which utilize the oxidizing hydroxyl radical ({sup {center_dot}O}H) and reducing aqueous electron (e{sup -}{sub aq}), to degrade chemical contaminants are alternatives to traditional water treatment methods, and are alternatives as water reuse becomes more generally implemented. Four major statin pharmaceuticals, fluvastatin, lovastatin, pravastatin and simvastatin, were studied, and the absolute bimolecular reaction rate constants with {sup {center_dot}O}H determined, (6.96{+-}0.16)x10{sup 9}, (2.92{+-}0.06)x10{sup 9}, (4.16{+-}0.13)x10{sup 9}, and (3.13{+-}0.15)x10{sup 9} M{sup -1} s{sup -1}, and for e{sup -}{sub aq} (2.31{+-}0.06)x10{sup 9}, (0.45{+-}0.01)x10{sup 9}, (1.26{+-}0.01)x10{sup 9}, and (0.69{+-}0.02)x10{sup 9} M{sup -1} s{sup -1}, respectively. To provide additional information on the radicals formed upon oxidation, transient spectra were measured and the overall reaction efficiency determined. Radical-based destruction mechanisms for destruction of the statins are proposed based on the LC-MS determination of the stable reaction by-products formed using {sup 137}Cs {gamma}-irradiation of statin solutions. Knowing the reaction rates, reaction efficiencies and destruction mechanisms of these compounds is essential for the consideration of the use of advanced oxidation/reduction processes for the destruction of statins in aqueous systems.

  4. The behavior of exciplex decay processes and interplay of radiationless transition and preliminary reorganization mechanisms of electron transfer in loose and tight pairs of reactants.

    Science.gov (United States)

    Kuzmin, Michael G; Soboleva, Irina V; Dolotova, Elena V

    2007-01-18

    Exciplex emission spectra and rate constants of their decay via internal conversion and intersystem crossing are studied and discussed in terms of conventional radiationless transition approach. Exciplexes of 9-cyanophenanthrene with 1,2,3-trimethoxybenzene and 1,3,5-trimethoxybenzene were studied in heptane, toluene, butyl acetate, dichloromethane, butyronitrile, and acetonitrile. A better description of spectra and rate constants is obtained using 0-0 transition energy and Gauss broadening of vibrational bands rather than the free energy of electron transfer and reorganization energy. The coincidence of parameters describing exciplex emission spectra and dependence of exciplex decay rate constants on energy gap gives the evidence of radiationless quantum transition mechanism rather than thermally activated medium reorganization mechanism of charge recombination in exciplexes and excited charge transfer complexes (contact radical ion pairs) as well as in solvent separated radical ion pairs. Radiationless quantum transition mechanism is shown to provide an appropriate description also for the main features of exergonic excited-state charge separation reactions if fast mutual transformations of loose and tight pairs of reactants are considered. In particular, very fast electron transfer (ET) in tight pairs of reactants with strong electronic coupling of locally excited and charge transfer states can prevent the observation of an inverted region in bimolecular excited-state charge separation even for highly exergonic reactions.

  5. Genome-Wide Bimolecular Fluorescence Complementation-Based Proteomic Analysis of Toxoplasma gondii ROP18’s Human Interactome Shows Its Key Role in Regulation of Cell Immunity and Apoptosis

    Directory of Open Access Journals (Sweden)

    Jing Xia

    2018-02-01

    Full Text Available Toxoplasma gondii rhoptry protein ROP18 (TgROP18 is a key virulence factor secreted into the host cell during invasion, where it modulates the host cell response by interacting with its host targets. However, only a few TgROP18 targets have been identified. In this study, we applied a high-throughput protein–protein interaction (PPI screening in human cells using bimolecular fluorescence complementation (BiFC to identify the targets of Type I strain ROP18 (ROP18I and Type II strain ROP18 (ROP18II. From a pool of more than 18,000 human proteins, 492 and 141 proteins were identified as the targets of ROP18I and ROP18II, respectively. Gene ontology, search tool for the retrieval of interacting genes/proteins PPI network, and Ingenuity pathway analyses revealed that the majority of these proteins were associated with immune response and apoptosis. This indicates a key role of TgROP18 in manipulating host’s immunity and cell apoptosis, which might contribute to the immune escape and successful parasitism of the parasite. Among the proteins identified, the immunity-related proteins N-myc and STAT interactor, IL20RB, IL21, ubiquitin C, and vimentin and the apoptosis-related protein P2RX1 were further verified as ROP18I targets by sensitized emission-fluorescence resonance energy transfer (SE-FRET and co-immunoprecipitation. Our study substantially contributes to the current limited knowledge on human targets of TgROP18 and provides a novel tool to investigate the function of parasite effectors in human cells.

  6. Development of organic membrane and biosensor. ; Artificial membrane chemical sensor on the model of olfactory cells. Seitaimaku to bio sensor no hatten. ; Kyusaibo wo model to shita jinkomaku kagaku sensor

    Energy Technology Data Exchange (ETDEWEB)

    Enomoto, S; Kashiwayanagi, M; Kurihara, K [Hokkaido University, Sapporo (Japan). Faculty of Pharmaceutical Science

    1991-05-05

    The olfactory cell is the most prominent chemical sensor to detect various kinds of external chemical substances with high sensibility. Consequently, on the model of such an organic chemical sensor mechanism, an artificial membrane with functions to detect and distinguish various chemical substances has been developed. In this study, a test using a lipid bimolecular membrane was carried out. As a result, it was found that the lipid bimolecular membrane showed membrane potential changes responding to various odorants. The mambrane with proper lipid composition presented almost the same sensibility to odorants as an olfactory organ. Response characteristic against various odors changed greatly due to the lipid composition and the addition of protein. It was also found that various odors can be discriminated by analyzing response information obtained from a lot of mambranes with different compositions Such ideas can be applied to the odor discrimination of the artificial membrane sensor. 14 refs., 13 figs.

  7. Charge transport in quantum dot organic solar cells with Si quantum dots sandwiched between poly(3-hexylthiophene) (P3HT) absorber and bathocuproine (BCP) transport layers

    Science.gov (United States)

    Verma, Upendra Kumar; Kumar, Brijesh

    2017-10-01

    We have modeled a multilayer quantum dot organic solar cell that explores the current-voltage characteristic of the solar cell whose characteristics can be tuned by varying the fabrication parameters of the quantum dots (QDs). The modeled device consists of a hole transport layer (HTL) which doubles up as photon absorbing layer, several quantum dot layers, and an electron transport layer (ETL). The conduction of charge carriers in HTL and ETL has been modeled by the drift-diffusion transport mechanism. The conduction and recombination in the quantum dot layers are described by a system of coupled rate equations incorporating tunneling and bimolecular recombination. Analysis of QD-solar cells shows improved device performance compared to the similar bilayer and trilayer device structures without QDs. Keeping other design parameters constant, solar cell characteristics can be controlled by the quantum dot layers. Bimolecular recombination coefficient of quantum dots is a prime factor which controls the open circuit voltage (VOC) without any significant reduction in short circuit current (JSC).

  8. Photoconductivity studies of the ferrocyanide ion under high pressure

    Energy Technology Data Exchange (ETDEWEB)

    Finston, M. I.

    1979-01-01

    The photoaquation of the ferrocyanide ion was studied using a high-pressure photoconductivity apparatus and a steady-state high-pressure mercury lamp. The first-order photocurrent rise-time could be related to the relative quantum efficiency of the photoaquation process, while the dark decay of the photocurrent yielded a relative value of the bimolecular rate-constant for the reverse reaction. Kinetic measurements were carried out on dilute solutions of potassium ferrocyanide in pure water, and in 20% ethanol. The photocurrent yield in aqueous solution was dependent upon secondary chemical equilibria which were sensitive to pressure in a predictable way. In ethanolic solution, the dependence of photocurrent yield on pressure followed the variation of the reciprocal solvent vicosity. In both aqueous and alcoholic solution, the photoaquation quantum efficiency decreased exponentially with pressure, as did the biomolecular rate-constant for the dark reaction in aqueous solution. The pressure dependence of the bimolecular rate-constant in the alcoholic solution indicated a diffusion-limited process. The pressure dependence of the photoaquation quantum yield, and of the bimolecular rate-constant in aqueous solution, was interpreted in terms of an activation volume model. The photoaquation data for both the aqueous and the alcoholic solutions agreed with a hypothetical mechanism whereby ligand-to-metal bond-breaking, and solvent-to-metal bond-formation, are effectively simultaneous. The results for the aqueous dark reaction strongly indicated breaking of the solvent-to-metal bond as the rate-limiting step.

  9. Cure and mechanical properties of carboxylated nitrile rubber (XNBR) vulcanized by alkaline earth metal compounds

    Science.gov (United States)

    Tulyapitak, Tulyapong

    Compounds of carboxylated nitrile rubber (XNBR) with alkaline metal oxides and hydroxide were prepared, and their cure and mechanical properties were investigated. Magnesium oxide (MgO) with different specific surface areas (45, 65, and 140 m2/g) was used. Increased specific surface area and concentration of MgO resulted in higher cure rate. Optimum stiffness, tensile strength, and ultimate strain required an equimolar amount of acidity and MgO. The effect of specific surface area on tensile properties was not significant. Crosslink density of XNBR-MgO vulcanizates increased with increased amounts of MgO. ATR-IR spectroscopy showed that neutralization occurs in two steps: (1) During mixing and storage, MgO reacts with carboxyl groups (RCOOH) to give RCOOMgOH. (2) Upon curing, these react bimolecularly to form RCOOMgOOCR and Mg(OH)2. Dynamic mechanical thermal analysis revealed an ionic transition at higher temperature, in addition to the glass transition. The ionic transition shifts to higher temperature with increasing MgO concentration. Like MgO-XNBR systems, cure rates of XNBR-calcium hydroxide (Ca(OH)2) and XNBR-barium oxide (BaO) compounds increased with increased content of curing agents. Curing by these two agents resulted in ionic crosslinks. To ensure optimum tensile properties, equimolar amounts of carboxyl groups and curing agents were required. Dynamic mechanical analysis revealed the ionic transition in these two systems. It shifted to higher temperature with increased amounts of curing agents. In contrast to MgO, Ca(OH)2, and BaO, calcium oxide (CaO) gave results similar to those for thermally cured samples. No ionic transition was observed in XNBR-CaO systems. Tensile strength of XNBR depended on the strength of ionic crosslinks, which was dependent on the size of the alkaline metal ions.

  10. Fluorescence quenching of fluorescein by Merocyanine 540 in liposomes

    International Nuclear Information System (INIS)

    Toprak, Mahmut; Meryem Aydin, Burcu; Arik, Mustafa; Onganer, Yavuz

    2011-01-01

    The fluorescence quenching of fluorescein (FL) by merociyanine 540 (MC540) was examined in L-egg lecithin phosphatidycholine (PC) liposomes using spectroscopic methods. The type of quenching mechanism (dynamic or static) was evaluated using the Stern-Volmer plots. Findings were also supported by the temperature studies and florescence decay measurements. The Stern-Volmer equation was utilized to calculate bimolecular quenching constants (K q ). Furthermore, the bimolecular quenching constant of the quencher in the liposomes (K SV ), partition coefficient (K p ), binding constant (K), and corresponding thermodynamic parameters ΔH, ΔS, and ΔG were calculated. The quenching property was also used in determining quantitatively (K p ) the partition coefficient of Merociyanini 540 in PC liposome.The obtained data indicated that static quenching occurred in the system and the K SV values decreased with increasing lipid concentration. In addition, thermodynamic analysis suggested that van der Waals interactions and hydrogen bonding were the main acting forces between fluorescein and merociyanine 540 molecules in the medium. - Highlights: → Fluorescence quenching of FL by MC540 in liposome system was analyzed. → Fluorescence quenching mechanism of FL by MC540 was consistent with the static model. → Binding FL to MC540 was spontaneous and carried out by hydrogen bond and van der Waals forces.

  11. The mechanism of ureido-pyrimidinone:2,7-diamido-naphthyridine complexation and the presence of kinetically controlled pathways in multicomponent hydrogen-bonded systems

    OpenAIRE

    de Greef, T.F.A.; Ligthart, G.B.W.L.; Lutz, M.; Spek, A.L.; Meijer, E.W.

    2008-01-01

    The kinetics of association of ureido-pyrimidinone (U) dimers, present either in the 4[1H]-keto form or in the pyrimidin-4-ol form, with 2,7-diamido-1,8-naphthyridine (N) into a complementary heterodimer have been investigated. The formation of heterodimers with 2,7-diamido-1,8-naphthyridine from pyrimidin- 4-ol dimers is much faster than from 4[1H]-pyrimidinone dimers. Using a combination of simple measurements and simulations, evidence for a bimolecular tautomerization step is presented. Fi...

  12. UV-initiated template copolymerization of AM and MAPTAC: Microblock structure, copolymerization mechanism, and flocculation performance.

    Science.gov (United States)

    Li, Xiang; Zheng, Huaili; Gao, Baoyu; Sun, Yongjun; Liu, Bingzhi; Zhao, Chuanliang

    2017-01-01

    Flocculation as the core technology of sludge pretreatment can improve the dewatering performance of sludge that enables to reduce the cost of sludge transportation and the subsequent disposal costs. Therefore, synthesis of high-efficiency and economic flocculant is remarkably desired in this field. This study presents a cationic polyacrylamide (CPAM) flocculant with microblock structure synthesized through ultraviolet (UV)-initiated template copolymerization by using acrylamide (AM) and methacrylamido propyl trimethyl ammonium chloride (MAPTAC) as monomers, sodium polyacrylate (PAAS) as template, and 2,2'-azobis [2-(2-imidazolin-2-yl) propane] dihydrochloride (VA-044) as photoinitiator. The microblock structure of the CPAM was observed through nuclear magnetic resonance ( 1 H NMR and 13 C NMR) spectroscopy, Fourier transform infrared (FTIR) spectroscopy, and scanning electron microscopy (SEM) analyses. Furthermore, thermogravimetric/differential scanning calorimetry (TG/DSC) analysis was used to evaluate its thermal decomposition property. The copolymerization mechanism was investigated through the determination of the binding constant M K and study on polymerization kinetics. Results showed that the copolymerization was conducted in accordance with the I (ZIP) template polymerization mechanism, and revealed the coexistence of bimolecular termination free-radical reaction and mono-radical termination in the polymerization process. Results of sludge dewatering tests indicated the superior flocculation performance of microblock flocculant than random distributed CPAM. The residual turbidity, filter cake moisture content, and specific resistance to filtration reached 9.37 NTU, 68.01%, and 6.24 (10 12  m kg -1 ), respectively, at 40 mg L -1 of template poly(AM-MAPTAC) and pH 6.0. Furthermore, all flocculant except commercial CPAM showed a wide scope of pH application. Copyright © 2016 Elsevier Ltd. All rights reserved.

  13. Single-molecule force-conductance spectroscopy of hydrogen-bonded complexes

    DEFF Research Database (Denmark)

    Pirrotta, Alessandro; De Vico, Luca; Solomon, Gemma C.

    2017-01-01

    to inform about molecular recognition events at the single-molecule limit. For this, we consider the force-conductance characteristics of a prototypical class of hydrogen bonded bimolecular complexes sandwiched between gold electrodes. The complexes consist of derivatives of a barbituric acid and a Hamilton...... is mechanically manipulated. The implication is that force and conductance provide complementary information about the evolution of molecules in junctions that can be used to interrogate basic structure-transport relations at the single-molecule limit....

  14. Ultrafast Photoinduced Electron Transfer in Bimolecular Donor-Acceptor Systems

    KAUST Repository

    Alsulami, Qana A.

    2016-11-30

    The efficiency of photoconversion systems, such as organic photovoltaic (OPV) cells, is largely controlled by a series of fundamental photophysical processes occurring at the interface before carrier collection. A profound understanding of ultrafast interfacial charge transfer (CT), charge separation (CS), and charge recombination (CR) is the key determinant to improving the overall performances of photovoltaic devices. The discussion in this dissertation primarily focuses on the relevant parameters that are involved in photon absorption, exciton separation, carrier transport, carrier recombination and carrier collection in organic photovoltaic devices. A combination of steady-state and femtosecond broadband transient spectroscopies was used to investigate the photoinduced charge carrier dynamics in various donor-acceptor systems. Furthermore, this study was extended to investigate some important factors that influence charge transfer in donor-acceptor systems, such as the morphology, energy band alignment, electronic properties and chemical structure. Interestingly, clear correlations among the steady-state measurements, time-resolved spectroscopy results, grain alignment of the electron transporting layer (ETL), carrier mobility, and device performance are found. In this thesis, we explored the significant impacts of ultrafast charge separation and charge recombination at donor/acceptor (D/A) interfaces on the performance of a conjugated polymer PTB7-Th device with three fullerene acceptors: PC71BM, PC61BM and IC60BA. Time-resolved laser spectroscopy and high-resolution electron microscopy can illustrate the basis for fabricating solar cell devices with improved performances. In addition, we studied the effects of the incorporation of heavy metals into π-conjugated chromophores on electron transfer by monitoring the triplet state lifetime of the oligomer using transient absorption spectroscopy, as understanding the mechanisms controlling intersystem crossing and

  15. Chemical kinetics of gas reactions

    CERN Document Server

    Kondrat'Ev, V N

    2013-01-01

    Chemical Kinetics of Gas Reactions explores the advances in gas kinetics and thermal, photochemical, electrical discharge, and radiation chemical reactions. This book is composed of 10 chapters, and begins with the presentation of general kinetic rules for simple and complex chemical reactions. The next chapters deal with the experimental methods for evaluating chemical reaction mechanisms and some theories of elementary chemical processes. These topics are followed by discussions on certain class of chemical reactions, including unimolecular, bimolecular, and termolecular reactions. The rema

  16. Nanoparticle Nucleation Is Termolecular in Metal and Involves Hydrogen: Evidence for a Kinetically Effective Nucleus of Three {Ir3H2x·P2W15Nb3O62}6- in Ir(0)n Nanoparticle Formation From [(1,5-COD)IrI·P2W15Nb3O62]8- Plus Dihydrogen.

    Science.gov (United States)

    Özkar, Saim; Finke, Richard G

    2017-04-19

    The nucleation process yielding Ir(0) ∼300 nanoparticles from (Bu 4 N) 5 Na 3 [(1,5-COD)Ir·P 2 W 15 Nb 3 O 62 ] (abbreviated hereafter as (COD)Ir·POM 8- , where POM 9- = the polyoxometalate, P 2 W 15 Nb 3 O 62 9- ) under H 2 is investigated to learn the true molecularity, and hence the associated kinetically effective nucleus (KEN), for nanoparticle formation for the first time. Recent work with this prototype transition-metal nanoparticle formation system ( J. Am. Chem. Soc. 2014 , 136 , 17601 - 17615 ) revealed that nucleation in this system is an apparent second-order in the precatalyst, A = (COD)Ir·POM 8- , not the higher order implied by classic nucleation theory and its nA ⇌ A n , "critical nucleus", A n concept. Herein, the three most reasonable more intimate mechanisms of nucleation are tested: bimolecular nucleation, termolecular nucleation, and a mechanism termed "alternative termolecular nucleation" in which 2(COD)Ir + and 1(COD)Ir·POM 8- yield the transition state of the rate-determining step of nucleation. The results obtained definitively rule out a simple bimolecular nucleation mechanism and provide evidence for the alternative termolecular mechanism with a KEN of 3, Ir 3 . All higher molecularity nucleation mechanisms were also ruled out. Further insights into the KEN and its more detailed composition involving hydrogen, {Ir 3 H 2x POM} 6- , are also obtained from the established role of H 2 in the Ir(0) ∼300 formation balanced reaction stoichiometry, from the p(H 2 ) dependence of the kinetics, and from a D 2 /H 2 kinetic isotope effect of 1.2(±0.3). Eight insights and conclusions are presented. A section covering caveats in the current work, and thus needed future studies, is also included.

  17. Bimolecular reaction of CH3 + CO in solid p-H2: Infrared absorption of acetyl radical (CH3CO) and CH3-CO complex

    Science.gov (United States)

    Das, Prasanta; Lee, Yuan-Pern

    2014-06-01

    We have recorded infrared spectra of acetyl radical (CH3CO) and CH3-CO complex in solid para-hydrogen (p-H2). Upon irradiation at 248 nm of CH3C(O)Cl/p-H2 matrices, CH3CO was identified as the major product; characteristic intense IR absorption features at 2990.3 (ν9), 2989.1 (ν1), 2915.6 (ν2), 1880.5 (ν3), 1419.9 (ν10), 1323.2 (ν5), 836.6 (ν7), and 468.1 (ν8) cm-1 were observed. When CD3C(O)Cl was used, lines of CD3CO at 2246.2 (ν9), 2244.0 (ν1), 1866.1 (ν3), 1046.7 (ν5), 1029.7 (ν4), 1027.5 (ν10), 889.1 (ν6), and 723.8 (ν7) cm-1 appeared. Previous studies characterized only three vibrational modes of CH3CO and one mode of CD3CO in solid Ar. In contrast, upon photolysis of a CH3I/CO/p-H2 matrix with light at 248 nm and subsequent annealing at 5.1 K before re-cooling to 3.2 K, the CH3-CO complex was observed with characteristic IR features at 3165.7, 3164.5, 2150.1, 1397.6, 1396.4, and 613.0 cm-1. The assignments are based on photolytic behavior, observed deuterium isotopic shifts, and a comparison of observed vibrational wavenumbers and relative IR intensities with those predicted with quantum-chemical calculations. This work clearly indicates that CH3CO can be readily produced from photolysis of CH3C(O)Cl because of the diminished cage effect in solid p-H2 but not from the reaction of CH3 + CO because of the reaction barrier. Even though CH3 has nascent kinetic energy greater than 87 kJ mol-1 and internal energy ˜42 kJ mol-1 upon photodissociation of CH3I at 248 nm, its energy was rapidly quenched so that it was unable to overcome the barrier height of ˜27 kJ mol-1 for the formation of CH3CO from the CH3 + CO reaction; a barrierless channel for formation of a CH3-CO complex was observed instead. This rapid quenching poses a limitation in production of free radicals via bimolecular reactions in p-H2.

  18. Mechanism of charge recombination in meso-structured organic-inorganic hybrid perovskite solar cells: A macroscopic perspective

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Wenchao; Yao, Yao, E-mail: yaoyao@fudan.edu.cn; Wu, Chang-Qin, E-mail: cqw@fudan.edu.cn [State Key Laboratory of Surface Physics and Department of Physics, Fudan University, Shanghai 200433 (China); Collaborative Innovation Center of Advanced Microstructures, Fudan University, Shanghai 200433 (China)

    2015-04-21

    In the currently popular organic-inorganic hybrid perovskite solar cells, the slowness of the charge recombination processes is found to be a key factor for contributing to their high efficiencies and high open circuit voltages, but the underlying recombination mechanism remains unclear. In this work, we investigate the bimolecular recombination (BR) and the trap-assisted monomolecular recombination (MR) in meso-structured perovskite solar cells under steady state working condition, and try to reveal their roles on determining the device performance. Some interfacial effects such as the injection barriers at the selective contacts are examined as well. Based on the macroscopic device modeling, the recombination resistance-voltage (R{sub rec}−V) and the current density-voltage (J–V) curves are calculated to characterize the recombination mechanism and describe the device performance, respectively. Through comparison with the impedance spectroscopy extracted R{sub rec} data, it is found that under the typical BR reduction factor and deep trap densities observed in experiments, the MR dominates the charge recombination in the low voltage regime, while the BR dominates in the high voltage regime. The short circuit current and the fill factor could be reduced by the significant MR but the open circuit voltage is generally determined by the BR. The different electron injection barriers at the contact can change the BR rate and induce different patterns for the R{sub rec}–V characteristics. For the perovskites of increased band gaps, the R{sub rec}'s are significantly enhanced, corresponding to the high open circuit voltages. Finally, it is revealed that the reduced effective charge mobility due to the transport in electron and hole transporting material makes the R{sub rec} decrease slowly with the increasing voltage, which leads to increased open circuit voltage.

  19. Rotational laser cooling of vibrationally and translationally cold molecular ions

    DEFF Research Database (Denmark)

    Staanum, Peter; Højbjerre, Klaus; Skyt, Peter Sandegaard

    2010-01-01

    Stationary molecules in well-defined internal states are of broad interest for physics and chemistry. In physics, this includes metrology 1, 2, 3 , quantum computing 4, 5 and many-body quantum mechanics 6, 7 , whereas in chemistry, state-prepared molecular targets are of interest for uni......-molecular reactions with coherent light fields 8, 9 , for quantum-state-selected bi-molecular reactions 10, 11, 12 and for astrochemistry 12 . Here, we demonstrate rotational ground-state cooling of vibrationally and translationally cold MgH+ ions, using a laser-cooling scheme based on excitation of a single...

  20. Direct Observation of Molecular Preorganization for Chirality Transfer on a Catalyst Surface

    DEFF Research Database (Denmark)

    Demers-Carpentier, Vincent; Goubert,, Guillaume; Masini, Federico

    2011-01-01

    The chemisorption of specific optically active compounds on metal surfaces can create catalytically active chirality transfer sites. However, the mechanism through which these sites bias the stereoselectivity of reactions (typically hydrogenations) is generally assumed to be so complex that conti......The chemisorption of specific optically active compounds on metal surfaces can create catalytically active chirality transfer sites. However, the mechanism through which these sites bias the stereoselectivity of reactions (typically hydrogenations) is generally assumed to be so complex...... functional theory calculations reveals the stereodirecting forces governing preorganization into precise chiral modifier-substrate bimolecular surface complexes. The study shows that the chiral modifier induces prochiral switching on the surface and that different prochiral ratios prevail at different...

  1. Radiolysis of uracil in oxygenated aqueous solutions. A study by product analysis and pulse radiolysis. [Gamma radiation

    Energy Technology Data Exchange (ETDEWEB)

    Schuchnmann, M N; Sonntag, C von [Max-Planck-Institut fuer Kohlenforschung, Muelheim an der Ruhr (Germany, F.R.). Inst. fuer Strahlenchemie

    1983-10-01

    Hydroxyl radicals are generated by the radiolysis of N/sub 2/O-O/sub 2/ (4:1 v/v)-saturated aqueous solutions of uracil. They add to the 5,6-double bond of the substrate. These radicals are converted by oxygen into the corresponding peroxyl radicals (I) and (II), respectively. Peroxyl radical (I) undergoes a base-induced O/sub 2//sup -/ elimination. As an intermediate 5-hydroxyisopyrimidine is formed which rearranges into isobarbituric acid and adds water forming 5,6-dihydro-5,6-dihydroxyuracil. Competing with this base-induced reaction of radical (I) there is a bimolecular decay of radicals (I) and (II). These processes become predominant at low pH. For this reason a strong pH dependence of G (products) is observed. The major products are (G values at pH 3 and 10 in parentheses) 5,6-dihydroxy-5,6-dihydrouracil (1.1; 2.4), isobarbituric acid (0; 1.2), N-formyl-5-hydroxyhydantoin (1.6; 0.2), 5-hydroxybarbituric acid (0.9; 0.2). 5-Hydroxybarbituric acid is formed in its keto form. Its deprotonation has been followed by pulse conductometry. Details of the reaction mechanism, e.g. the involvement of oxyl radicals in the bimolecular decay of (I) and (II), are discussed.

  2. The radiolysis of uracil in oxygenated aqueous solutions. A study by product analysis and pulse radiolysis

    International Nuclear Information System (INIS)

    Schuchnmann, M.N.; Sonntag, C. von

    1983-01-01

    Hydroxyl radicals are generated by the radiolysis of N 2 O-O 2 (4:1 v/v)-saturated aqueous solutions of uracil. They add to the 5,6-double bond of the substrate. These radicals are converted by oxygen into the corresponding peroxyl radicals (I) and (II), respectively. Peroxyl radical (I) undergoes a base-induced O 2 - elimination. As an intermediate 5-hydroxyisopyrimidine is formed which rearranges into isobarbituric acid and adds water forming 5,6-dihydro-5,6-dihydroxyuracil. Competing with this base-induced reaction of radical (I) there is a bimolecular decay of radicals (I) and (II). These processes become predominant at low pH. For this reason a strong pH dependence of G (products) is observed. The major products are (G values at pH 3 and 10 in parentheses) 5,6-dihydroxy-5,6-dihydrouracil (1.1; 2.4), isobarbituric acid (0; 1.2), N-formyl-5-hydroxyhydantoin (1.6; 0.2), 5-hydroxybarbituric acid (0.9; 0.2). 5-Hydroxybarbituric acid is formed in its keto form. Its deprotonation has been followed by pulse conductometry. Details of the reaction mechanism, e.g. the involvement of oxyl radicals in the bimolecular decay of (I) and (II), are discussed. (author)

  3. Radiation-induced destruction of organic compounds in aqueous solutions by dual oxidation/reduction mechanism

    Energy Technology Data Exchange (ETDEWEB)

    Chaychiana, M.; Silverman, J.; Al-Sheikhly, M. [Department of Materials Science and Engineering, University of Maryland (United States); Poster, D.; Neta, P.; Huie, R. [Chemical Science and Technology Laboratory, National Institute of Standard and Technology (United States)

    2011-07-01

    This research presents the feasibility and mechanisms of using high energy electrons for the dechlorination of polychlorinated biphenyls (PCBs) in marine sediment, and hazardous organic compounds in waste water. The remediation of the organic contaminants by ionizing radiation is achieved by means of both reduction and oxidation processes. PCBs in marine sediment can be effectively dechlorinated by reduction, while toxic organic compounds in water are removed mainly by oxidation. Radiolytic degradation of aqueous suspensions of PCBs in marine sediments in the presence of isopropanol was also studied. Addition of isopropanol was necessary to enhance the radiolytic yield and the dechlorination of PCBs. Also presented are results from an examination of the oxidative and reductive effects of electron-beam irradiation on the concentrations of six organic solvents in water. The organic solvents in water were prepared to mimic a pharmaceutical waste stream. Radiation-induced destruction of benzene was also investigated using pulse radiolysis technique. Pulse radiolysis with spectrophotometric and conductometric detection was utilized to study the formation and reactions of radicals from benzene and dienes in aqueous solutions. The benzene OH adduct, {sup ●}C{sub 6}H{sub 6}OH, reacts with O{sub 2} (k = 3x10{sup 8} L mol{sup -1} s{sup -1}) in a reversible reaction. The peroxyl radical, HOC{sub 6}H{sub 6}O{sub 2}{sup ●}, undergoes O{sub 2}●- elimination, bimolecular decay, and reaction with benzene to initiate a chain reaction, depending on the dose rate, benzene concentration, and pH. The occurrence of the chain reaction is demonstrated in low-dose-rate gamma radiolysis experiments where the consumption of O{sub 2} was monitored. (author)

  4. Radiation-chemical reaction of 2,3,5-triphenyl-tetrazolium chloride in liquid and solid state

    DEFF Research Database (Denmark)

    Kovacs, A.; Wojnarovits, L.; McLaughlin, W.L.

    1996-01-01

    In pulse radiolysis of 2,3,5-triphenyl-tetrazolium chloride (TTC) at around 360 nm fast formation of intermediate tetrazolium radical was observed under both oxidizing and reducing conditions. In the latter case bimolecular formation of formazan, absorbing at around 480 nm, was observed. This rea......In pulse radiolysis of 2,3,5-triphenyl-tetrazolium chloride (TTC) at around 360 nm fast formation of intermediate tetrazolium radical was observed under both oxidizing and reducing conditions. In the latter case bimolecular formation of formazan, absorbing at around 480 nm, was observed...

  5. Chain propagation and termination mechanisms for polymerization of conjugated polar alkenes by [Al]-based frustrated Lewis pairs

    KAUST Repository

    He, Jianghua

    2014-11-25

    A combined experimental and theoretical study on mechanistic aspects of polymerization of conjugated polar alkenes by frustrated Lewis pairs (FLPs) based on N-heterocyclic carbene (NHC) and Al(C6F5)3 pairs is reported. This study consists of three key parts: structural characterization of active propagating intermediates, propagation kinetics, and chain-termination pathways. Zwitterionic intermediates that simulate the active propagating species in such polymerization have been generated or isolated from the FLP activation of monomers such as 2-vinylpyridine and 2-isopropenyl-2-oxazoline-one of which, IMes+-CH2C(Me)=(C3H2NO)Al(C6F5)3 - (2), has been structurally characterized. Kinetics performed on the polymerization of 2-vinylpyridine by ItBu/Al(C6F5)3 revealed that the polymerization follows a zero-order dependence on monomer concentration and a first-order dependence on initiator (ItBu) and activator [Al(C6F5)3] concentrations, indicating a bimolecular, activated monomer propagation mechanism. The Lewis pair polymerization of conjugate polar alkenes such as methacrylates is accompanied by competing chain-termination side reactions; between the two possible chain-termination pathways, the one that proceeds via intramolecular backbiting cyclization involving nucleophilic attack of the activated ester group of the growing polymer chain by the O-ester enolate active chain end to generate a six-membered lactone (δ-valerolactone)-terminated polymer chain is kinetically favored, but thermodynamically disfavored, over the pathway leading to the -ketoester-terminated chain, as revealed by computational studies.

  6. Light illumination intensity dependence of photovoltaic parameter in polymer solar cells with ammonium heptamolybdate as hole extraction layer.

    Science.gov (United States)

    Liu, Zhiyong; Niu, Shengli; Wang, Ning

    2018-01-01

    A low-temperature, solution-processed molybdenum oxide (MoO X ) layer and a facile method for polymer solar cells (PSCs) is developed. The PSCs based on a MoO X layer as the hole extraction layer (HEL) is a significant advance for achieving higher photovoltaic performance, especially under weaker light illumination intensity. Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) measurements show that the (NH 4 ) 6 Mo 7 O 24 molecule decomposes and forms the molybdenum oxide (MoO X ) molecule when undergoing thermal annealing treatment. In this study, PSCs with the MoO X layer as the HEL exhibited better photovoltaic performance, especially under weak light illumination intensity (from 100 to 10mWcm -2 ) compared to poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS)-based PSCs. Analysis of the current density-voltage (J-V) characteristics at various light intensities provides information on the different recombination mechanisms in the PSCs with a MoO X and PEDOT:PSS layer as the HEL. That the slopes of the open-circuit voltage (V OC ) versus light illumination intensity plots are close to 1 unity (kT/q) reveals that bimolecular recombination is the dominant and weaker monomolecular recombination mechanism in open-circuit conditions. That the slopes of the short-circuit current density (J SC ) versus light illumination intensity plots are close to 1 reveals that the effective charge carrier transport and collection mechanism of the MoO X /indium tin oxide (ITO) anode is the weaker bimolecular recombination in short-circuit conditions. Our results indicate that MoO X is an alternative candidate for high-performance PSCs, especially under weak light illumination intensity. Copyright © 2017 Elsevier Inc. All rights reserved.

  7. Experimental and theoretical examples of the value and limitations of transition state theory

    International Nuclear Information System (INIS)

    Golden, D.M.

    1979-01-01

    Value and limitations of transition-state theory (TST) are reviewed. TST analyses of the temperature dependence of the ''direct'' reactions CH 3 + CH 3 CHO → CH 4 + CH 3 CO (1) and O + CH 4 → OH + CH 3 (2) are presented in detail, and other examples of TST usefulness are recalled. Limitations are discussed for bimolecular processes in terms of ''complex'' vs ''direct'' mechanisms. The reaction OH + CO → CO 2 + H is discussed in this context. Limitations for unimolecular processes seem to arise only for simple bond fission processes, and recent advances are noted. 2 figures, 5 tables

  8. Experimental and theoretical examples of the value and limitations of transition state theory

    Science.gov (United States)

    Golden, D. M.

    1979-01-01

    Value and limitations of transition-state theory (TST) are reviewed. TST analyses of the temperature dependence of the 'direct' reactions CH3 + CH3CHO yields CH4 + CH3CO(1) and O + CH4 yields OH + CH3(2) are presented in detail, and other examples of TST usefulness are recalled. Limitations are discussed for bimolecular processes in terms of 'complex' vs. 'direct' mechanisms. The reaction OH + CO yields CO2 + H is discussed in this context. Limitations for unimolecular processes seem to arise only for simple bond fission processes, and recent advances are noted.

  9. Factors Governing Intercalation of Fullerenes and Other Small Molecules Between the Side Chains of Semiconducting Polymers Used in Solar Cells

    KAUST Repository

    Miller, Nichole Cates

    2012-08-22

    While recent reports have established signifi cant miscibility in polymer:fullerene blends used in organic solar cells, little is actually known about why polymers and fullerenes mix and how their mixing can be controlled. Here, X-ray diffraction (XRD), differential scanning calorimetry (DSC), and molecular simulations are used to study mixing in a variety of polymer:molecule blends by systematically varying the polymer and smallmolecule properties. It is found that a variety of polymer:fullerene blends mix by forming bimolecular crystals provided there is suffi cient space between the polymer side chains to accommodate a fullerene. Polymer:tetrafl uoro-tetracyanoquinodimethane (F4-TCNQ) bimolecular crystals were also observed, although bimolecular crystals did not form in the other studied polymer:nonfullerene blends, including those with both conjugated and non-conjugated small molecules. DSC and molecular simulations demonstrate that strong polymer-fullerene interactions can exist, and the calculations point to van der Waals interactions as a signifi cant driving force for molecular mixing. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Effect of applied hydrostatic pressure on the quenching kinetics, and electronic and molecular structure of eight and nine-coordinate lanthanide complexes in solution

    International Nuclear Information System (INIS)

    Maupin, C.L.; Riehl, J.P.

    1998-01-01

    Full text: Applied hydrostatic pressure may be used as a probe of the reaction mechanism for various solution reactions involving lanthanide ions. In this work we report on the use of high pressure to probe the mechanism of enantioselective quenching between racemic luminescent lanthanide complexes containing Dy(III) Tb(III) and Eu(III), and optically active transition metal complexes as quenchers. Diastereomeric rate constants are obtained from a biexponential fit of the luminescence decay. Particular attention will be given to solvation effects on the measured diastereomeric rate constants. The source of chirality is ascribed to a enantioselective rearrangement step within a bimolecular 'encounter' complex yielding a intermolecular geometry in which the energy transfer is efficient. The effect of high pressure on the molecular and electronic structure of these complexes will also be discussed

  11. Effects of gamma irradiation on polypropylene, polypropylene + high density polyethylene and polypropylene + high density polyethylene + wood flour

    Energy Technology Data Exchange (ETDEWEB)

    Reyes, J.; Albano, C.; Davidson, E.; Poleo, R. [Universidad Central de Venezuela, Caracas (Venezuela). Escuela de Quimica; Gonzalez, J.; Ichazo, M. [Universidad Simon Bolivar, Dept. de Mecanica, Caracas (Venezuela); Chipara, M. [Research Institute for Electrotechnics, Bucharest (Romania)

    2001-04-01

    The effect of the gamma-irradiation on the mechanical properties of the composites, Polypropylene (PP), PP+high density Polyethylene (HDPE), PP+ HDPE+wood flour, where HDPE is virgin and recycled, was studied. This paper discusses the behavior of the composites after exposure to various doses of gamma irradiation (1-7 MRads) in the presence of oxygen. The dependence of mechanical properties on the integral dose for a constant dose rate of 0.48 MRads/h confirms the influence of the irradiation. Strong effects on the elongation at break and break strength is noticed. The mathematical analysis suggests for the PP+r-HDPE a bimolecular process of the elongation at break. On the order hand, for the PP+HDPE a complex process is represented for a three exponential equation. (orig.)

  12. Effects of gamma irradiation on polypropylene, polypropylene + high density polyethylene and polypropylene + high density polyethylene + wood flour

    International Nuclear Information System (INIS)

    Reyes, J.; Albano, C.; Davidson, E.; Poleo, R.; Chipara, M.

    2001-01-01

    The effect of the gamma-irradiation on the mechanical properties of the composites, Polypropylene (PP), PP+high density Polyethylene (HDPE), PP+ HDPE+wood flour, where HDPE is virgin and recycled, was studied. This paper discusses the behavior of the composites after exposure to various doses of gamma irradiation (1-7 MRads) in the presence of oxygen. The dependence of mechanical properties on the integral dose for a constant dose rate of 0.48 MRads/h confirms the influence of the irradiation. Strong effects on the elongation at break and break strength is noticed. The mathematical analysis suggests for the PP+r-HDPE a bimolecular process of the elongation at break. On the order hand, for the PP+HDPE a complex process is represented for a three exponential equation. (orig.)

  13. Fluorescence and optical absorption in spodumene

    International Nuclear Information System (INIS)

    Antonini, R.

    1987-01-01

    This work studied the mechanism of the isothermal decay's kinetic of the 15.600 cm-1 optical absorption band (A.O.) of irradiated spodumene, and the phosphorescence of irradiated spodumene in low temperatures. The kinetic mechanisms applying the bimolecular model to liberation, capture and recombination reactions are analysed. The coupled differential equations, resultants of this model, numerically using the Runge-Kutta method is solved, and a computer programs that allowed determine the kinetics parameters by try and error methods is developped. This work showed that the electrons are untrapped according to Arrhernios kinetic and that the parameters of the trap and recombination are proportional to a factor (√T - √T o ), where T o is the cutting temperature, bfore which the reactions do not occur. (author) [pt

  14. Solar upconversion with plasmon-enhanced bimolecular complexes

    Energy Technology Data Exchange (ETDEWEB)

    Dionne, Jennifer [Stanford Univ., CA (United States)

    2017-04-14

    Upconversion of sub-bandgap photons is a promising approach to exceed the Shockley-Queisser limit in solar technologies. However, due to the low quantum efficiencies and narrow absorption bandwidths of upconverters, existing systems have only led to fractional percent improvements in photovoltaic devices (~0.01%). In this project, we aimed to develop an efficient upconverting material that could improve cell efficiencies by at least one absolute percent. To achieve this goal, we first used thermodynamic calculations to determine cell efficiencies with realistic upconverting materials. Then, we designed, synthesized, and characterized nanoantennas that promise >100x enhancement in both the upconverter absorption cross-section and emissive radiative rate. Concurrently, we optimized the upconverer by designing new ionic and molecular complexes that promise efficient solid-state upconversion. Lastly, with Bosch, we simulated record-efficiency semi-transparent cells that will allow for ready incorporation of our upconverting materials. While we were not successful in designing record efficiency upconverters during our three years of funding, we gained significant insight into the existing limitations of upconverters and how to best address these challenges. Ongoing work is aimed at addressing these limitations, to make upconversion a cost-competitive solar technology in future years.

  15. NITRITE REDUCTASE ACTIVITY OF NON-SYMBIOTIC HEMOGLOBINS FROM ARABIDOPSIS THALIANA†

    Science.gov (United States)

    Tiso, Mauro; Tejero, Jesús; Kenney, Claire; Frizzell, Sheila; Gladwin, Mark T.

    2013-01-01

    Plant non-symbiotic hemoglobins possess hexa-coordinate heme geometry similar to the heme protein neuroglobin. We recently discovered that deoxygenated neuroglobin converts nitrite to nitric oxide (NO), an important signaling molecule involved in many processes in plants. We sought to determine whether Arabidopsis thaliana non-symbiotic hemoglobins class 1 and 2 (AHb1 and AHb2) might function as nitrite reductases. We found that the reaction of nitrite with deoxygenated AHb1 and AHb2 generates NO gas and iron-nitrosyl-hemoglobin species. The bimolecular rate constants for nitrite reduction to NO are 19.8 ± 3.2 and 4.9 ± 0.2 M−1s−1, at pH = 7.4 and 25°C, respectively. We determined the pH dependence of these bimolecular rate constants and found a linear correlation with the concentration of protons, indicating the requirement for one proton in the reaction. Release of free NO gas during reaction in anoxic and hypoxic (2% oxygen) conditions was confirmed by chemiluminescence detection. These results demonstrate that deoxygenated AHb1 and AHb2 reduce nitrite to form NO via a mechanism analogous to that observed for hemoglobin, myoglobin and neuroglobin. Our findings suggest that during severe hypoxia and in the anaerobic plant roots, especially in water submerged species, non-symbiotic hemoglobins provide a viable pathway for NO generation via nitrite reduction. PMID:22620259

  16. Dissociation dynamics of CH3I in electric spark induced breakdown revealed by time-resolved laser induced breakdown spectroscopy

    International Nuclear Information System (INIS)

    Wang, Yang; Liu, Wei-long; Song, Yun-fei; Duo, Li-ping; Liu, Yu-qiang; Yang, Yan-qiang

    2015-01-01

    Highlights: • Emission of electric spark dissociation of CH 3 I is similar to its fs LIBS. • We use fs laser induced breakdown as a simulation for electric spark dissociation. • The I 2 molecule formation is directly observed in the time-resolved LIBS. • Bimolecular collision of I ∗ and CH 3 I is responsible for the formation of I 2 . - Abstract: The electric discharge spark dissociation of gas CH 3 I is found to be similar to its femtosecond laser photodissociation. The almost identical spectra of the two processes show that their initial ionization conditions are very similar. The initial ionization followed by molecular fragmentation is proposed as the dissociation mechanism, in which the characteristic emissions of I + , CH 3 , CH 2 , CH, H, and I 2 are identified as the dissociation products. The emission band of 505 nm I 2 is clearly observed in the time-resolved laser induced breakdown spectroscopy (LIBS). The dynamic curve indicates that I 2 ∗ molecules are formed after the delay time of ∼4.7 ns. The formation of I 2 ∗ molecule results from the bimolecular collision of the highly excited iodine atom I ∗ ( 4 P) and CH 3 I molecule. This dynamical information can help understand the process of electric discharge spark dissociation of CH 3 I

  17. A Versatile Platform to Analyze Low-Affinity and Transient Protein-Protein Interactions in Living Cells in Real Time

    Directory of Open Access Journals (Sweden)

    Yao-Cheng Li

    2014-12-01

    Full Text Available Summary: Protein-protein interactions (PPIs play central roles in orchestrating biological processes. While some PPIs are stable, many important ones are transient and hard to detect with conventional approaches. We developed ReBiL, a recombinase enhanced bimolecular luciferase complementation platform, to enable detection of weak PPIs in living cells. ReBiL readily identified challenging transient interactions between an E3 ubiquitin ligase and an E2 ubiquitin-conjugating enzyme. ReBiL’s ability to rapidly interrogate PPIs in diverse conditions revealed that some stapled α-helical peptides, a class of PPI antagonists, induce target-independent cytosolic leakage and cytotoxicity that is antagonized by serum. These results explain the requirement for serum-free conditions to detect stapled peptide activity, and define a required parameter to evaluate for peptide antagonist approaches. ReBiL’s ability to expedite PPI analysis, assess target specificity and cell permeability, and reveal off-target effects of PPI modifiers should facilitate the development of effective, cell-permeable PPI therapeutics and the elaboration of diverse biological mechanisms. : Li et al. developed a recombinase-enhanced bimolecular luciferase complementation platform, termed ReBiL, to evaluate low-affinity protein-protein interactions (PPIs that are not detectable by other methods and to analyze PPI antagonists in living cells. ReBiL showed that small-molecule p53-Mdm2 antagonists disrupt their intended targets effectively in cells, whereas stapled peptides did not. Stapled peptides unexpectedly induced cell membrane disruption resulting in p53-independent death associated with cytoplasmic leakage. ReBiL is also valuable for high-throughput screening and for deciphering signaling mechanisms mediated by protein interactions.

  18. Electron transfer kinetics of cytochrome c immobilized on a phenolic terminated thiol self assembled monolayer determined by scanning electrochemical microscopy

    International Nuclear Information System (INIS)

    Alizadeh, Vali; Mousavi, Mir Fazlollah; Mehrgardi, Masoud Ayatollahi; Kazemi, Sayed Habib; Sharghi, Hashem

    2011-01-01

    Highlights: → Preparing a thiolated phenolic self-assembled monolayer surface (SAM). → Application of this SAM to immobilize cytochrome C. → Scanning electrochemical microscopy used for these studies. → Determination of both tunneling electron transfer and bimolecular rate constants between the immobilized protein-substrate and probe. - Abstract: In the present manuscript, the electrochemical behavior of cytochrome c (cyt-c) immobilized onto a phenolic terminated self assembled monolayer (SAM) on a gold electrode is investigated using cyclic voltammetry (CV) and scanning electrochemical microscopy (SECM). The tunneling electron transfer (ET) rate constant between the immobilized protein and the underlying electrode surface, and also the bimolecular ET rate constant between the immobilized protein and a probe has been obtained using approach curves that were obtained by SECM. The approach curves were recorded at different substrate overpotentials in the presence of various concentrations of ferrocyanide as a probe and various surface concentrations of cyt-c; then the standard tunneling ET and bimolecular rate constants are obtained as 3.4 ± 0.3 s -1 and (2.0 ± 0.5) x 10 7 cm 3 mol -1 s -1 , respectively.

  19. Electron transfer kinetics of cytochrome c immobilized on a phenolic terminated thiol self assembled monolayer determined by scanning electrochemical microscopy

    Energy Technology Data Exchange (ETDEWEB)

    Alizadeh, Vali [Department of Chemistry, Tarbiat Modares University, P.O. Box 14115-175, Tehran (Iran, Islamic Republic of); Mousavi, Mir Fazlollah, E-mail: mousavim@modares.ac.ir [Department of Chemistry, Tarbiat Modares University, P.O. Box 14115-175, Tehran (Iran, Islamic Republic of); Mehrgardi, Masoud Ayatollahi [Department of Chemistry, University of Isfahan, Isfahan (Iran, Islamic Republic of); Kazemi, Sayed Habib [Department of Chemistry, Institute for Advanced Studies in Basic Sciences (IASBS), Zanjan (Iran, Islamic Republic of); Sharghi, Hashem [Department of Chemistry, Shiraz University, Shiraz (Iran, Islamic Republic of)

    2011-07-01

    Highlights: > Preparing a thiolated phenolic self-assembled monolayer surface (SAM). > Application of this SAM to immobilize cytochrome C. > Scanning electrochemical microscopy used for these studies. > Determination of both tunneling electron transfer and bimolecular rate constants between the immobilized protein-substrate and probe. - Abstract: In the present manuscript, the electrochemical behavior of cytochrome c (cyt-c) immobilized onto a phenolic terminated self assembled monolayer (SAM) on a gold electrode is investigated using cyclic voltammetry (CV) and scanning electrochemical microscopy (SECM). The tunneling electron transfer (ET) rate constant between the immobilized protein and the underlying electrode surface, and also the bimolecular ET rate constant between the immobilized protein and a probe has been obtained using approach curves that were obtained by SECM. The approach curves were recorded at different substrate overpotentials in the presence of various concentrations of ferrocyanide as a probe and various surface concentrations of cyt-c; then the standard tunneling ET and bimolecular rate constants are obtained as 3.4 {+-} 0.3 s{sup -1} and (2.0 {+-} 0.5) x 10{sup 7} cm{sup 3} mol{sup -1} s{sup -1}, respectively.

  20. Investigation of molecular mechanisms in photodynamic action and radiobiology with nanosecond flash photolysis and pulse radiolysis. Progress report, July 1, 1974--June 30, 1975

    International Nuclear Information System (INIS)

    Grossweiner, L.I.

    1975-01-01

    Initial mechanisms in the UV photooxidation of aromatic amino acids are being investigated with laser flash photolysis at 265 nm in connection with enzyme inactivation. Aqueous tryptophan (Trp) is photoionized by an efficient monophotonic process, followed by a hitherto unreported pseudo-first order recombination competing with bimolecular e - /sub aq/ decay and electron scavengers. Measurements of the photoionization quantum efficiency, the aromatic radical extinction coefficients, and the electron decay kinetics are reported. The flash photolysis of N-formylkynurenine (FK) has been studied in connection with its role in ''internal'' photodynamic action in bovine carbonic anhydrase (BCA). The triplet state of FK oxidizes Trp to the radical formed also by UV photolysis, leading to the FK semiquinone which reacts with oxygen to produce O 2 - . The same FK semiquinone species is formed by radiolytic reduction by e - /sub aq/ and CO 2 - . A parallel radiolysis study on BCA using radical anions as probes of specific residues has shown that the zinc atom protects against the inactivating attack of e - /sub aq/ and CO 2 - . Evidence for sensitive aromatic residues in BCA has been found with this technique. Photodynamic damage to biological membranes is being studied with spin label ESR methods. New work is reported on damage to unsaturated lipids sensitized by Eosin based on changes in the temperature-dependence of the spin label rotational correlation time. Preliminary results with diploid yeast membranes (Saccharomyces cerevisiae) show a loosening of the structure accompanying photodynamic inactivation. (U.S.)

  1. Electron transfer reactions of metal complexes in solution

    International Nuclear Information System (INIS)

    Sutin, N.

    1977-01-01

    A few representative electron-transfer reactions are selected and their kinetic parameters compared with the predictions of activated complex models. Since Taube has presented an elegant treatment of intramolecular electron-transfer reactions, emphasis is on bimolecular reactions. The latter electron-transfer reactions are more complicated to treat theoretically since the geometries of their activated complexes are not as well known as for the intramolecular case. In addition in biomolecular reactions, the work required to bring the two reactants together needs to be calculated. Since both reactants generally carry charges this presents a non-trivial problem at the ionic strengths usually used to study bimolecular electron transfer

  2. Kinetics and Mechanism of Bioactivation via S-Oxygenation of Anti-Tubercular Agent Ethionamide by Peracetic Acid.

    Science.gov (United States)

    Chipiso, Kudzanai; Logan, Isabelle E; Eskew, Matthew W; Omondi, Benard; Simoyi, Reuben H

    2016-10-11

    The kinetics and mechanism of the oxidation of the important antitubercular agent, ethionamide, ETA (2-ethylthioisonicotinamide), by peracetic acid (PAA) have been studied. It is effectively a biphasic reaction with an initial rapid first phase of the reaction which is over in about 5 s and a second slower phase of the reaction which can run up to an hour. The first phase involves the addition of a single oxygen atom to ethionamide to form the S-oxide. The second phase involves further oxidation of the S-oxide to desulfurization of ETA to give 2-ethylisonicotinamide. In contrast to the stability of most organosulfur compounds, the S-oxide of ETA is relatively stable and can be isolated. In conditions of excess ETA, the stoichiometry of the reaction was strictly 1:1: CH 3 CO 3 H + Et(C 5 H 4 )C(═S)NH 2 → CH 3 CO 2 H + Et(C 5 H 4 )C(═NH)SOH. In this oxidation, it was apparent that only the sulfur center was the reactive site. Though ETA was ultimately desulfurized, only the S-oxide was stable. Electrospray ionization (ESI) spectral analysis did not detect any substantial formation of the sulfinic and sulfonic acids. This suggests that cleavage of the carbon-sulfur bond occurs at the sulfenic acid stage, resulting in the formation of an unstable sulfur species that can react further to form more stable sulfur species. In this oxidation, no sulfate formation was observed. ESI spectral analysis data showed a final sulfur species in the form of a dimeric sulfur monoxide species, H 3 S 2 O 2 . We derived a bimolecular rate constant for the formation of the S-oxide of (3.08 ± 0.72) × 10 2 M -1 s -1 . Oxidation of the S-oxide further to give 2-ethylisonicotinamide gave zero order kinetics.

  3. Consequences of thermo- and photo-oxidation on end-use properties of pure PE

    International Nuclear Information System (INIS)

    Tireau, Jonathan; Van Schoors, Laetitia; Benzarti, Karim; Colin, Xavier

    2010-01-01

    Thin films of polyethylene have been exposed to thermal and photochemical accelerated agings at different temperatures and different UV intensities. In both cases, mechanical tests performed on aged samples revealed a severe embrittlement of the PE material. However, a multi-scale analysis showed that i) under thermal oxidative conditions, such embrittlement mainly resulted from a reduction of molecular mobility of the amorphous phase due to annealing phenomena, while ii) it was rather associated to a competition between chain scission and cross-linking processes under photo-oxidative conditions. As regards the oxidation mechanisms, it was found that thermo-oxidation is clearly initiated by a bimolecular decomposition of hydroperoxides, while photo-oxidation seems rather initiated by the photolysis of ketones and hydroperoxides. Over a critical threshold of the hydroperoxide concentration, thermolysis of hydroperoxides seems to predominate and even to control the overall photo-oxidation kinetics.

  4. Mass spectrometric studies of bimolecular reactions in a selected ion flow tube (SIFT)

    International Nuclear Information System (INIS)

    Shul, R.J.; Upschulte, B.L.; Passarella, R.; Keesee, R.G.; Castleman, A.W.

    1985-01-01

    The rate coefficients for a number of thermal energy charge transfer reactions have been obtained with a selected ion flow tube (SIFT). The reactions studied involve Ar + and Ar 2 + with a variety of neutral molecules including: O 2 , CS 2 , CO 2 , SO 2 , H 2 S, NH 3 , and SF 6 . Such reactions have been of long-standing interest in the field of gas-phase ion-molecule chemistry from both a practical and fundamental point of view. Consideration of charge transfer reactions as possible sources of chemical lasers and their role in ionospheric and interstellar chemistry account for much of the interest. Fundamentally, the mechanism involved in these reactions has yet to be definitively established. The consumption deposition of energy into internal modes and translational degrees of freedom in such reactions has also been a topic of considerable debate. The apparatus consists of five main components: an ion source, SIFT quadrupole, ion injector, flow tube, and a mass spectrometer detection system. Ions formed in a high pressure source leak into a SIFT quadrupole where they are mass selected. The primary ion of interest is then injected into the flow tube where reactions are studied. Once in the flow tube the ions are carried downstream by an inert buffer gas, either argon, nitrogen, or helium in the present study. Neutral reactant gas is added through a reactant gas inlet (RGI) at an appropriate location downstream in the flow tube, and allowed to react with the injected ions. Ions on the flow tube axis are sampled through a 1 mm orifice where they are mass analyzed by a second quadrupole mass spectrometer and detected with a channeltron electron multiplier

  5. A computational perspective of vibrational and electronic analysis of potential photosensitizer 2-chlorothioxanthone

    Science.gov (United States)

    Ali, Narmeen; Mansha, Asim; Asim, Sadia; Zahoor, Ameer Fawad; Ghafoor, Sidra; Akbar, Muhammad Usman

    2018-03-01

    This paper deals with combined theoretical and experimental study of geometric, electronic and vibrational properties of 2-chlorothioxanthone (CTX) molecule which is potential photosensitizer. The FT-IR spectrum of CTX in solid phase was recorded in 4000-400 cm-1 region. The UV-Vis. absorption spectrum was also recorded in the laboratory as well as computed at DFT/B3LYP level in five different phases viz. gas, water, DMSO, acetone and ethanol. The quantum mechanics based theoretical IR and Raman spectra were also calculated for the title compound employing HF and DFT functional with 3-21G+, 6-31G+ and 6-311G+, 6-311G++ basis sets, respectively, and assignment of each vibrational frequency has been done on the basis of potential energy distribution (PED). A comparison has been made between theoretical and experimental vibrational spectra as well as for the UV-Vis. absorption spectra. The computed infra red & Raman spectra by DFT compared with experimental spectra along with reliable vibrational assignment based on PED. The calculated electronic properties, results of natural bonding orbital (NBO) analysis, charge distribution, dipole moment and energies have been reported in the paper. Bimolecular quenching of triplet state of CTX in the presence of triethylamine, 2-propanol triethylamine and diazobicyclooctane (DABCO) reflect the interactions between them. The bimolecular quenching rate constant is fastest for interaction of 3CTX in the presence of DABCO reflecting their stronger interactions.

  6. The molecular mechanism underlying anthocyanin metabolism in apple using the MdMYB16 and MdbHLH33 genes.

    Science.gov (United States)

    Xu, Haifeng; Wang, Nan; Liu, Jingxuan; Qu, Changzhi; Wang, Yicheng; Jiang, Shenghui; Lu, Ninglin; Wang, Deyun; Zhang, Zongying; Chen, Xuesen

    2017-05-01

    MdMYB16 forms homodimers and directly inhibits anthocyanin synthesis via its C-terminal EAR repressor. It weakened the inhibitory effect of MdMYB16 on anthocyanin synthesis when overexpressing MdbHLH33 in callus overexpressing MdMYB16. MdMYB16 could interact with MdbHLH33. Anthocyanins are strong antioxidants that play a key role in the prevention of cardiovascular disease, cancer, and diabetes. The germplasm of Malus sieversii f. neidzwetzkyana is important for the study of anthocyanin metabolism. To date, only limited studies have examined the negative regulatory mechanisms underlying anthocyanin synthesis in apple. Here, we analyzed the relationship between anthocyanin levels and MdMYB16 expression in mature Red Crisp 1-5 apple (M. domestica) fruit, generated an evolutionary tree, and identified an EAR suppression sequence and a bHLH binding motif of the MdMYB16 protein using protein sequence analyses. Overexpression of MdMYB16 or MdMYB16 without bHLH binding sequence (LBSMdMYB16) in red-fleshed callus inhibited MdUFGT and MdANS expression and anthocyanin synthesis. However, overexpression of MdMYB16 without the EAR sequence (LESMdMYB16) in red-fleshed callus had no inhibitory effect on anthocyanin. The yeast one-hybrid assay showed that MdMYB16 and LESMdMYB16 interacted the promoters of MdANS and MdUFGT, respectively. Yeast two-hybrid, pull-down, and bimolecular fluorescence complementation assays showed that MdMYB16 formed homodimers and interacted with MdbHLH33, however, the LBSMdMYB16 could not interact with MdbHLH33. We overexpressed MdbHLH33 in callus overexpressing MdMYB16 and found that it weakened the inhibitory effect of MdMYB16 on anthocyanin synthesis. Together, these results suggested that MdMYB16 and MdbHLH33 may be important part of the regulatory network controlling the anthocyanin biosynthetic pathway.

  7. Bimolecular recombination in ambipolar organic field effect transistors

    NARCIS (Netherlands)

    Charrier, D. S. H.; de Vries, T.; Mathijssen, S. G. J.; Geluk, E. -J.; Smits, E. C. P.; Kemerink, M.; Janssen, R. A. J.

    In ambipolar organic field effect transistors (OFET) the shape of the channel potential is intimately related to the recombination zone width W, and hence to the electron-hole recombination strength. Experimentally, the recombination profile can be assessed by scanning Kelvin probe microscopy

  8. Bimolecular recombination in ambipolar organic field effect transistors

    NARCIS (Netherlands)

    Charrier, D.S.H.; Vries, T. de; Mathijssen, S.G.J.; Geluk, E.-J.; Smits, E.C.P.; Kemerink, M.; Janssen, R.A.J.

    2009-01-01

    In ambipolar organic field effect transistors (OFET) the shape of the channel potential is intimately related to the recombination zone width W, and hence to the electron–hole recombination strength. Experimentally, the recombination profile can be assessed by scanning Kelvin probe microscopy

  9. Construction of a bimolecular fluorescence complementation (BiFC ...

    African Journals Online (AJOL)

    DR. NJ TONUKARI

    2012-08-02

    Aug 2, 2012 ... Accepted 8 June, 2012. Protein–protein interactions are essential for signal transduction in cells. ... BiFC is a novel technology that is used for identifying .... occasional fluorescence was observed, it was very weak ... Light field.

  10. Non-Langevin bimolecular recombination in low-mobility materials

    Czech Academy of Sciences Publication Activity Database

    Juška, G.; Arlauskas, K.; Stuchlík, Jiří; Österbacka, R.

    2006-01-01

    Roč. 352, - (2006), s. 1167-1171 ISSN 0022-3093 Institutional research plan: CEZ:AV0Z10100521 Keywords : solar cells * photovoltaics * polymers and organics Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.362, year: 2006

  11. Recipe for attaining optimal energy resolution in inorganic scintillators

    Energy Technology Data Exchange (ETDEWEB)

    Singh, Jai; Koblov, Alexander [School of Engineering and IT, B-purple-12, Faculty of EHSE, Charles Darwin University, Darwin, NT 0909 (Australia)

    2012-12-15

    Using an approximate form of the density of excitation created within the track initiated by an incident {gamma} - photon on a scintillator, the light yield is derived as a function of linear, bimolecular and Auger radiative and quenching recombination rates. The non-proportionality in the yield is analysed as a function of the bimolecular and Auger quenching rates and also its dependence on the track radius is studied. An optimal combination of these quenching rates and track radius is presented to obtain a recipe for inventing a scintillator material with optimal energy resolution. The importance of the mobility of charge carriers in minimising the non-proportionality in a scintillator is also discussed (copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  12. Kinetic aspects of the syntheses using short-lived radionuclides

    International Nuclear Information System (INIS)

    Laangstroem, B.; Obenius, U.; Sjoeberg, S.; Bergson, G.

    1981-01-01

    In syntheses using short-lived radionuclides, such as 11 C, the reaction conditions are usually such that the concentrations of the reactants, except for the labelled reactant, can be considered constant during the reaction. Two kinetic models have been investigated - irreversible and reversible bimolecular elementary reactions. The influence of the rate constants, of the equilibrium constants, and of the ratio between the starting reactants on the yield of the labelled product has been studied. The results show that, even in cases with unfavourable equilibrium constants, high yields of the labelled products can be obtained if the rate constant for the forward reaction is large. In addition, the specific activity of the labelled product as a function of time has been studied for the irreversible bimolecular case. (author)

  13. Recipe for attaining optimal energy resolution in inorganic scintillators

    International Nuclear Information System (INIS)

    Singh, Jai; Koblov, Alexander

    2012-01-01

    Using an approximate form of the density of excitation created within the track initiated by an incident γ - photon on a scintillator, the light yield is derived as a function of linear, bimolecular and Auger radiative and quenching recombination rates. The non-proportionality in the yield is analysed as a function of the bimolecular and Auger quenching rates and also its dependence on the track radius is studied. An optimal combination of these quenching rates and track radius is presented to obtain a recipe for inventing a scintillator material with optimal energy resolution. The importance of the mobility of charge carriers in minimising the non-proportionality in a scintillator is also discussed (copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  14. Analysis of JP-10 Combustion Mechanism Based on Bimolecular Reaction Collision Model%气体介质中 JP-10液滴蒸发数值模拟研究

    Institute of Scientific and Technical Information of China (English)

    袁嵩; 于亮; 赵汝岩

    2016-01-01

    为了进一步了解 JP-10燃料在航空发动机燃烧室中的蒸发燃烧机理,基于 SRK 状态方程,运用数学建模的方法,对 JP-10液滴蒸发过程进行了数值模拟并分析了环境因素对液滴蒸发表面温度变化及液滴生存时间变化的影响。研究表明,气体介质与液滴间的相对速度和环境压力及温度对 JP-10液滴蒸发湿球温度、升温过程及生存时间影响明显。%In order to further understand the evaporation and combustion mechanism of the JP-10 droplet in the engine combustion chamber,based on the SRK state equation,and by means of mathematical modeling,we simulated the evaporation process of the JP-10 droplet and analyzed the influences of environmental factors on the droplet surface temperature and life time.The results show that the influences of ambient pressure and temperature and relative velocity between gas and droplet on the JP-10 evaporation wet-bulb temperature,heating process and survival time are obvious.

  15. Factors Governing Intercalation of Fullerenes and Other Small Molecules Between the Side Chains of Semiconducting Polymers Used in Solar Cells

    KAUST Repository

    Miller, Nichole Cates; Cho, Eunkyung; Gysel, Roman; Risko, Chad; Coropceanu, Veaceslav; Miller, Chad E.; Sweetnam, Sean; Sellinger, Alan; Heeney, Martin; McCulloch, Iain; Bré das, Jean-Luc; Toney, Michael F.; McGehee, Michael D.

    2012-01-01

    bimolecular crystals did not form in the other studied polymer:nonfullerene blends, including those with both conjugated and non-conjugated small molecules. DSC and molecular simulations demonstrate that strong polymer-fullerene interactions can exist

  16. Heterologous aggregates promote de novo prion appearance via more than one mechanism.

    Directory of Open Access Journals (Sweden)

    Fatih Arslan

    2015-01-01

    Full Text Available Prions are self-perpetuating conformational variants of particular proteins. In yeast, prions cause heritable phenotypic traits. Most known yeast prions contain a glutamine (Q/asparagine (N-rich region in their prion domains. [PSI+], the prion form of Sup35, appears de novo at dramatically enhanced rates following transient overproduction of Sup35 in the presence of [PIN+], the prion form of Rnq1. Here, we establish the temporal de novo appearance of Sup35 aggregates during such overexpression in relation to other cellular proteins. Fluorescently-labeled Sup35 initially forms one or a few dots when overexpressed in [PIN+] cells. One of the dots is perivacuolar, colocalizes with the aggregated Rnq1 dot and grows into peripheral rings/lines, some of which also colocalize with Rnq1. Sup35 dots that are not near the vacuole do not always colocalize with Rnq1 and disappear by the time rings start to grow. Bimolecular fluorescence complementation failed to detect any interaction between Sup35-VN and Rnq1-VC in [PSI+][PIN+] cells. In contrast, all Sup35 aggregates, whether newly induced or in established [PSI+], completely colocalize with the molecular chaperones Hsp104, Sis1, Ssa1 and eukaryotic release factor Sup45. In the absence of [PIN+], overexpressed aggregating proteins such as the Q/N-rich Pin4C or the non-Q/N-rich Mod5 can also promote the de novo appearance of [PSI+]. Similar to Rnq1, overexpressed Pin4C transiently colocalizes with newly appearing Sup35 aggregates. However, no interaction was detected between Mod5 and Sup35 during [PSI+] induction in the absence of [PIN+]. While the colocalization of Sup35 and aggregates of Rnq1 or Pin4C are consistent with the model that the heterologous aggregates cross-seed the de novo appearance of [PSI+], the lack of interaction between Mod5 and Sup35 leaves open the possibility of other mechanisms. We also show that Hsp104 is required in the de novo appearance of [PSI+] aggregates in a [PIN

  17. Modeling photocurrent transients in organic solar cells

    International Nuclear Information System (INIS)

    Hwang, I; Greenham, N C

    2008-01-01

    We investigate the transient photocurrents of organic photovoltaic devices in response to a sharp turn-on of illumination, by numerical modeling of the drift-diffusion equations. We show that the photocurrent turn-on dynamics are determined not only by the transport dynamics of free charges, but also by the time required for the population of geminate charge pairs to reach its steady-state value. The dissociation probability of a geminate charge pair is found to be a key parameter in determining the device performance, not only by controlling the efficiency at low intensities, but also in determining the fate of charge pairs formed by bimolecular recombination at high intensities. Bimolecular recombination is shown to reduce the turn-on time at high intensities, since the typical distance traveled by a charge pair is reduced.

  18. LOW TEMPERATURE FORMATION OF NITROGEN-SUBSTITUTED POLYCYCLIC AROMATIC HYDROCARBONS (PANHs)—BARRIERLESS ROUTES TO DIHYDRO(iso)QUINOLINES

    Energy Technology Data Exchange (ETDEWEB)

    Parker, Dorian S. N.; Yang, Tao; Dangi, Beni B.; Kaiser, Ralf I. [Department of Chemistry, University of Hawaii at Manoa, Honolulu, HI 96822 (United States); Bera, Partha P.; Lee, Timothy J., E-mail: ralfk@hawaii.edu, E-mail: Timothy.J.Lee@nasa.gov [Space Science and Astrobiology Division, NASA Ames Research Center, Moffett Field, Mountain View, CA 94035 (United States)

    2015-12-20

    Meteorites contain bio-relevant molecules such as vitamins and nucleobases, which consist of aromatic structures with embedded nitrogen atoms. Questions remain over the chemical mechanisms responsible for the formation of nitrogen-substituted polycyclic aromatic hydrocarbons (PANHs) in extraterrestrial environments. By exploiting single collision conditions, we show that a radical mediated bimolecular collision between pyridyl radicals and 1,3-butadiene in the gas phase forms nitrogen-substituted polycyclic aromatic hydrocarbons (PANHs) 1,4-dihydroquinoline and to a minor amount 1,4-dihydroisoquinoline. The reaction proceeds through the formation of a van der Waals complex, which circumnavigates the entrance barrier implying it can operate at very low kinetic energy and therefore at low temperatures of 10 K as present in cold molecular clouds such as TMC-1. The discovery of facile de facto barrierless exoergic reaction mechanisms leading to PANH formation could play an important role in providing a population of aromatic structures upon which further photo-processing of ice condensates could occur to form nucleobases.

  19. Ultrastable cellulosome-adhesion complex tightens under load.

    Science.gov (United States)

    Schoeler, Constantin; Malinowska, Klara H; Bernardi, Rafael C; Milles, Lukas F; Jobst, Markus A; Durner, Ellis; Ott, Wolfgang; Fried, Daniel B; Bayer, Edward A; Schulten, Klaus; Gaub, Hermann E; Nash, Michael A

    2014-12-08

    Challenging environments have guided nature in the development of ultrastable protein complexes. Specialized bacteria produce discrete multi-component protein networks called cellulosomes to effectively digest lignocellulosic biomass. While network assembly is enabled by protein interactions with commonplace affinities, we show that certain cellulosomal ligand-receptor interactions exhibit extreme resistance to applied force. Here, we characterize the ligand-receptor complex responsible for substrate anchoring in the Ruminococcus flavefaciens cellulosome using single-molecule force spectroscopy and steered molecular dynamics simulations. The complex withstands forces of 600-750 pN, making it one of the strongest bimolecular interactions reported, equivalent to half the mechanical strength of a covalent bond. Our findings demonstrate force activation and inter-domain stabilization of the complex, and suggest that certain network components serve as mechanical effectors for maintaining network integrity. This detailed understanding of cellulosomal network components may help in the development of biocatalysts for production of fuels and chemicals from renewable plant-derived biomass.

  20. Investigation of the fluorescence quenching of 2,3-diazabicyclo[2.2.2]oct-2-ene (DBO) by certain substituted uracils

    Energy Technology Data Exchange (ETDEWEB)

    Anbazhagan, V. [School of Chemistry, Bharathidasan University, Tiruchirappalli 620024, Tamil Nadu (India); Renganathan, R. [School of Chemistry, Bharathidasan University, Tiruchirappalli 620024, Tamil Nadu (India)], E-mail: rrengas@yahoo.com

    2009-04-15

    The fluorescence quenching of 2,3-diazabicyclo[2.2.2]oct-2-ene (DBO) by a series of uracils has been studied in water and acetonitrile solvents using steady-state and time-resolved fluorescence techniques. The steady-state fluorescence quenching technique has been performed in three different pHs (i.e. 4, 8 and 12). The bimolecular quenching rate constant (k{sub q}) increases with increase in pH of uracils. In acidic pH, a pure hydrogen atom abstraction is proposed as the quenching mechanism. This is supported by a pronounced solvent deuterium isotope effect. Electron transfer from the anionic form of uracil to the excited state of DBO is proposed as a mechanism for quenching in basic pH on the basis of highly exergonic thermodynamics obtained from the Rehm-Weller equation. The variation of k{sub q} is explained on the basis of the electronic effect of substitution in uracils as well.

  1. Investigation of the fluorescence quenching of 2,3-diazabicyclo[2.2.2]oct-2-ene (DBO) by certain substituted uracils

    International Nuclear Information System (INIS)

    Anbazhagan, V.; Renganathan, R.

    2009-01-01

    The fluorescence quenching of 2,3-diazabicyclo[2.2.2]oct-2-ene (DBO) by a series of uracils has been studied in water and acetonitrile solvents using steady-state and time-resolved fluorescence techniques. The steady-state fluorescence quenching technique has been performed in three different pHs (i.e. 4, 8 and 12). The bimolecular quenching rate constant (k q ) increases with increase in pH of uracils. In acidic pH, a pure hydrogen atom abstraction is proposed as the quenching mechanism. This is supported by a pronounced solvent deuterium isotope effect. Electron transfer from the anionic form of uracil to the excited state of DBO is proposed as a mechanism for quenching in basic pH on the basis of highly exergonic thermodynamics obtained from the Rehm-Weller equation. The variation of k q is explained on the basis of the electronic effect of substitution in uracils as well

  2. Efficient Photon Recycling and Radiation Trapping in Cesium Lead Halide Perovskite Waveguides

    KAUST Repository

    Dursun, Ibrahim; Zheng, Yangzi; Guo, Tianle; de Bastiani, Michele; Turedi, Bekir; Sinatra, Lutfan; Haque, Mohammed; Sun, Bin; Zhumekenov, Ayan A.; Saidaminov, Makhsud I.; Garcia de Arquer, F. Pelayo; Sargent, Edward H.; Wu, Tao; Gartstein, Yuri N; Bakr, Osman; Mohammed, Omar F.; Malko, Anton V.

    2018-01-01

    . At longer separations, the PL spectrum develops a red-shifted emission peak accompanied by an appearance of well-resolved rise times in the PL kinetics. We developed quantitative modeling that accounts for bimolecular recombination and photon recycling

  3. Modulating Excitonic Recombination Effects through One-Step Synthesis of Perovskite Nanoparticles for Light-Emitting Diodes.

    Science.gov (United States)

    Kulkarni, Sneha A; Muduli, Subas; Xing, Guichuan; Yantara, Natalia; Li, Mingjie; Chen, Shi; Sum, Tze Chien; Mathews, Nripan; White, Tim J; Mhaisalkar, Subodh G

    2017-10-09

    The primary advantages of halide perovskites for light-emitting diodes (LEDs) are solution processability, direct band gap, good charge-carrier diffusion lengths, low trap density, and reasonable carrier mobility. The luminescence in 3 D halide perovskite thin films originates from free electron-hole bimolecular recombination. However, the slow bimolecular recombination rate is a fundamental performance limitation. Perovskite nanoparticles could result in improved performance but processability and cumbersome synthetic procedures remain challenges. Herein, these constraints are overcome by tailoring the 3 D perovskite as a near monodisperse nanoparticle film prepared through a one-step in situ deposition method. Replacing methyl ammonium bromide (CH 3 NH 3 Br, MABr) partially by octyl ammonium bromide [CH 3 (CH 2 ) 7 NH 3 Br, OABr] in defined mole ratios in the perovskite precursor proved crucial for the nanoparticle formation. Films consisting of the in situ formed nanoparticles displayed signatures associated with excitonic recombination, rather than that of bimolecular recombination associated with 3 D perovskites. This transition was accompanied by enhanced photoluminescence quantum yield (PLQY≈20.5 % vs. 3.40 %). Perovskite LEDs fabricated from the nanoparticle films exhibit a one order of magnitude improvement in current efficiency and doubling in luminance efficiency. The material processing systematics derived from this study provides the means to control perovskite morphologies through the selection and mixing of appropriate additives. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Wave Mechanics or Wave Statistical Mechanics

    International Nuclear Information System (INIS)

    Qian Shangwu; Xu Laizi

    2007-01-01

    By comparison between equations of motion of geometrical optics and that of classical statistical mechanics, this paper finds that there should be an analogy between geometrical optics and classical statistical mechanics instead of geometrical mechanics and classical mechanics. Furthermore, by comparison between the classical limit of quantum mechanics and classical statistical mechanics, it finds that classical limit of quantum mechanics is classical statistical mechanics not classical mechanics, hence it demonstrates that quantum mechanics is a natural generalization of classical statistical mechanics instead of classical mechanics. Thence quantum mechanics in its true appearance is a wave statistical mechanics instead of a wave mechanics.

  5. [Epimerization of hydroxyl group in the lupan series of triterpenes].

    Science.gov (United States)

    Symon, A V; Kaplun, A P; Vlasenkova, N K; Gerasimova, G K; Shon, Le Bang; Litvin, E F; Kozlova, L M; Surkova, E L; Shvets, V I

    2003-01-01

    Two methods of obtaining of 3 alpha-betulinic acid and related compounds from their 3 beta-epimers were studied: the reaction of bimolecular substitution and the stereoselective reduction of 3-ketoderivatives. The substitution of acyloxy by formyloxy group in 3-O-tosyllupeol or of the betulin hydroxyl by benzoyloxy group resulted only in delta 2, 3-elimination products, with none of the expected products of bimolecular substitution being found. The catalytic hydrogenation of betulonic acid over Raney nickel resulted only in reduction of the isopropenyl double bond, whereas the use of 5% Ru/C gave a 60:40 mixture of epimers of dihydrobetulinic acid. Practically the same mixture of betulinic acid epimers was obtained when reducing betulonic acid with L-Selectride. The cytotoxic activity of 3 alpha-betulinic acid increased toward melanoma Bro cells and decreased toward melanoma MS cells.

  6. Dissection of the mechanism of manganese porphyrin-catalyzed chlorine dioxide generation.

    Science.gov (United States)

    Umile, Thomas P; Wang, Dong; Groves, John T

    2011-10-17

    Chlorine dioxide, an industrially important biocide and bleach, is produced rapidly and efficiently from chlorite ion in the presence of water-soluble, manganese porphyrins and porphyrazines at neutral pH under mild conditions. The electron-deficient manganese(III) tetra-(N,N-dimethyl)imidazolium porphyrin (MnTDMImP), tetra-(N,N-dimethyl)benzimidazolium (MnTDMBImP) porphyrin, and manganese(III) tetra-N-methyl-2,3-pyridinoporphyrazine (MnTM23PyPz) were found to be the most efficient catalysts for this process. The more typical manganese tetra-4-N-methylpyridiumporphyrin (Mn-4-TMPyP) was much less effective. Rates for the best catalysts were in the range of 0.24-32 TO/s with MnTM23PyPz being the fastest. The kinetics of reactions of the various ClO(x) species (e.g., chlorite ion, hypochlorous acid, and chlorine dioxide) with authentic oxomanganese(IV) and dioxomanganese(V)MnTDMImP intermediates were studied by stopped-flow spectroscopy. Rate-limiting oxidation of the manganese(III) catalyst by chlorite ion via oxygen atom transfer is proposed to afford a trans-dioxomanganese(V) intermediate. Both trans-dioxomanganese(V)TDMImP and oxoaqua-manganese(IV)TDMImP oxidize chlorite ion by 1-electron, generating the product chlorine dioxide with bimolecular rate constants of 6.30 × 10(3) M(-1) s(-1) and 3.13 × 10(3) M(-1) s(-1), respectively, at pH 6.8. Chlorine dioxide was able to oxidize manganese(III)TDMImP to oxomanganese(IV) at a similar rate, establishing a redox steady-state equilibrium under turnover conditions. Hypochlorous acid (HOCl) produced during turnover was found to rapidly and reversibly react with manganese(III)TDMImP to give dioxoMn(V)TDMImP and chloride ion. The measured equilibrium constant for this reaction (K(eq) = 2.2 at pH 5.1) afforded a value for the oxoMn(V)/Mn(III) redox couple under catalytic conditions (E' = 1.35 V vs NHE). In subsequent processes, chlorine dioxide reacts with both oxomanganese(V) and oxomanganese(IV)TDMImP to afford chlorate

  7. Femtosecond laser induced and controlled chemical reaction of carbon monoxide and hydrogen

    CSIR Research Space (South Africa)

    Du Plessis, A

    2011-07-01

    Full Text Available Results from experiments aimed at bimolecular chemical reaction control of CO and H2 at room temperature and pressure, without any catalyst, using shaped femtosecond laser pulses are presented. A stable reaction product (CO2) was measured after...

  8. Kinetics and Mechanism of the Reaction of Hydoxyl Radicals with Acetonitrile under Atmospheric Conditions

    Science.gov (United States)

    Hynes, A. J.; Wine, P. H.

    1997-01-01

    scheme to extract kinetic information about the adduct reations with O2 and branching ratios for OH regeneration. A plausible mechanism for OH regeneration in (2) involves OH addition to the nitrogen atom followed by O2 addition to the cyano carbon atom, isomeriazation and decomposition to D2CO + DOCN + OH. Our results suggest that the OH + CH3CN reaction occurs via a complex mechanism involving both bimolecular and termolecular pathways, analogous to the mechanisms for the the important atmospheric reactions of OH with CO and HNO3.

  9. Ultrafast Photoinduced Electron Transfer in Bimolecular Donor-Acceptor Systems

    KAUST Repository

    Alsulami, Qana

    2016-01-01

    , electronic properties and chemical structure. Interestingly, clear correlations among the steady-state measurements, time-resolved spectroscopy results, grain alignment of the electron transporting layer (ETL), carrier mobility, and device performance

  10. Single-molecule stochastic times in a reversible bimolecular reaction

    Science.gov (United States)

    Keller, Peter; Valleriani, Angelo

    2012-08-01

    In this work, we consider the reversible reaction between reactants of species A and B to form the product C. We consider this reaction as a prototype of many pseudobiomolecular reactions in biology, such as for instance molecular motors. We derive the exact probability density for the stochastic waiting time that a molecule of species A needs until the reaction with a molecule of species B takes place. We perform this computation taking fully into account the stochastic fluctuations in the number of molecules of species B. We show that at low numbers of participating molecules, the exact probability density differs from the exponential density derived by assuming the law of mass action. Finally, we discuss the condition of detailed balance in the exact stochastic and in the approximate treatment.

  11. BGK-type models in strong reaction and kinetic chemical equilibrium regimes

    International Nuclear Information System (INIS)

    Monaco, R; Bianchi, M Pandolfi; Soares, A J

    2005-01-01

    A BGK-type procedure is applied to multi-component gases undergoing chemical reactions of bimolecular type. The relaxation process towards local Maxwellians, depending on mass and numerical densities of each species as well as common velocity and temperature, is investigated in two different cases with respect to chemical regimes. These cases are related to the strong reaction regime characterized by slow reactions, and to the kinetic chemical equilibrium regime where fast reactions take place. The consistency properties of both models are stated in detail. The trend to equilibrium is numerically tested and comparisons for the two regimes are performed within the hydrogen-air and carbon-oxygen reaction mechanism. In the spatial homogeneous case, it is also shown that the thermodynamical equilibrium of the models recovers satisfactorily the asymptotic equilibrium solutions to the reactive Euler equations

  12. The radiochemistry of [18 F]-FDG: the first experience in Mexico

    International Nuclear Information System (INIS)

    Lopez D, F.A.

    2004-01-01

    The present work describes the more used method for the synthesis of 2 - [ 18 F] - fluorine-2-deoxy-D-glucose that is the more used radiopharmaceutical in the nuclear medicine in the cancer diagnostic. The process consists on two chemical reactions: i) [ 18 F - ] - nucleophilic radio fluorination and i i) a hydrolysis catalyzed by acid. The first reaction incorporates to the [ 18 F]- fluorine labelled inside the organic precursor 1,3,4,6-tetra- O -acetil-2- O-trifluoromethanesulfonyl- β-D-mannopyranose (triflate of mannose). The mechanism of this reaction is a bimolecular nucleophilic substitution (SN 2 ) with the ion [ 18 F - ] - fluoride; in the second reaction, the hydrolysis of those protective acetyl groups generate the hydroxyl groups free of the [ 18 F]-FDG. The process includes an azeotropic distillation and several purification steps. (Author)

  13. Live visualization of genomic loci with BiFC-TALE.

    Science.gov (United States)

    Hu, Huan; Zhang, Hongmin; Wang, Sheng; Ding, Miao; An, Hui; Hou, Yingping; Yang, Xiaojing; Wei, Wensheng; Sun, Yujie; Tang, Chao

    2017-01-11

    Tracking the dynamics of genomic loci is important for understanding the mechanisms of fundamental intracellular processes. However, fluorescent labeling and imaging of such loci in live cells have been challenging. One of the major reasons is the low signal-to-background ratio (SBR) of images mainly caused by the background fluorescence from diffuse full-length fluorescent proteins (FPs) in the living nucleus, hampering the application of live cell genomic labeling methods. Here, combining bimolecular fluorescence complementation (BiFC) and transcription activator-like effector (TALE) technologies, we developed a novel method for labeling genomic loci (BiFC-TALE), which largely reduces the background fluorescence level. Using BiFC-TALE, we demonstrated a significantly improved SBR by imaging telomeres and centromeres in living cells in comparison with the methods using full-length FP.

  14. Advanced Oxidation Degradation of Diclofenac

    International Nuclear Information System (INIS)

    Cooper, William J.; Song Weihua

    2012-01-01

    Advanced oxidation/reduction processes (AO/RPs), utilize free radical reactions to directly degrade chemical contaminants as an alternative to traditional water treatment. This study reports the absolute rate constants for reaction of diclofenac sodium and the model compound (2, 6-dichloraniline) with the two major AO/RP radicals; the hydroxyl radical (•OH) and hydrated electron (e - aq ). The bimolecular reaction rate constants (M -1 s -1 ) for diclofenac for •OH was (9.29 ± 0.11) x 10 9 , and, for e- aq was (1.53 ± 0.03) x10 9 . Preliminary degradation mechanisms are suggested based on product analysis using 60 Co γ-irradiation and LC-MS for reaction by-product identification. The toxicity of products was evaluated using the Vibrio fischeri luminescent bacteria method. (author)

  15. Charge carrier recombination dynamics in perovskite and polymer solar cells

    Energy Technology Data Exchange (ETDEWEB)

    Paulke, Andreas; Kniepert, Juliane; Kurpiers, Jona; Wolff, Christian M.; Schön, Natalie; Brenner, Thomas J. K.; Neher, Dieter [Institute of Physics and Astronomy, University of Potsdam, Karl-Liebknecht-Str. 24–25, 14476, Potsdam (Germany); Stranks, Samuel D. [Clarendon Laboratory, Department of Physics, University of Oxford, Parks Road, Oxford OX1 3PU (United Kingdom); Research Laboratory of Electronics, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139 (United States); Cavendish Laboratory, JJ Thomson Avenue, Cambridge CB3 0HE (United Kingdom); Snaith, Henry J. [Clarendon Laboratory, Department of Physics, University of Oxford, Parks Road, Oxford OX1 3PU (United Kingdom)

    2016-03-14

    Time-delayed collection field experiments are applied to planar organometal halide perovskite (CH{sub 3}NH{sub 3}PbI{sub 3}) based solar cells to investigate charge carrier recombination in a fully working solar cell at the nanosecond to microsecond time scale. Recombination of mobile (extractable) charges is shown to follow second-order recombination dynamics for all fluences and time scales tested. Most importantly, the bimolecular recombination coefficient is found to be time-dependent, with an initial value of ca. 10{sup −9} cm{sup 3}/s and a progressive reduction within the first tens of nanoseconds. Comparison to the prototypical organic bulk heterojunction device PTB7:PC{sub 71}BM yields important differences with regard to the mechanism and time scale of free carrier recombination.

  16. Probing Temperature-Dependent Recombination Kinetics in Polymer:Fullerene Solar Cells by Electric Noise Spectroscopy

    Directory of Open Access Journals (Sweden)

    Giovanni Landi

    2017-09-01

    Full Text Available The influence of solvent additives on the temperature behavior of both charge carrier transport and recombination kinetics in bulk heterojunction solar cells has been investigated by electric noise spectroscopy. The observed differences in charge carrier lifetime and mobility are attributed to a different film ordering and donor-acceptor phase segregation in the blend. The measured temperature dependence indicates that bimolecular recombination is the dominant loss mechanism in the active layer, affecting the device performance. Blend devices prepared with a high-boiling-point solvent additive show a decreased recombination rate at the donor-acceptor interface as compared to the ones prepared with the reference solvent. A clear correlation between the device performance and the morphological properties is discussed in terms of the temperature dependence of the mobility-lifetime product.

  17. Effect of regioregularity on recombination dynamics in inverted bulk heterojunction organic solar cells

    Science.gov (United States)

    Chandrasekaran, Naresh; Liu, Amelia C. Y.; Kumar, Anil; McNeill, Christopher R.; Kabra, Dinesh

    2018-01-01

    The effect of polymer regioregularity on the charge transport properties and bimolecular recombination rates of polymer-based solar cells is studied in detail using transient photovoltaic techniques. We compare organic solar cells fabricated with an ITO/ZnO/PEIE/P3HT:PCBM/MoO3/Ag structure using either 100% regioregular poly(3-hexylthiophene) (DF-P3HT) yielding an average power conversion efficiency (PCE) of 3.8  ±  0.3% or 92% regioregular P3HT (rr-P3HT) that yields an average PCE of 3.28  ±  0.4%. Transient photocurrent measurements reveal the presence of less mobile photoinduced charges in rr-P3HT:PCBM cells when compared to DF-P3HT:PCBM solar cells. Transient photovoltage measurements are used to establish the relationship between regioregularity and bimolecular recombination rate constant (k) finding that under 1 Sun, devices with high regioregularity have a longer τ despite having a higher k. The high value of k for the DF-P3HT:PCBM system as compared to the rr-P3HT:PCBM system is attributed to enhanced mobility and better charge transport of mobile charges in the DF-P3HT:PCBM system, consistent with enhanced fibrillar order in DF-P3HT films observed with transmission electron microscopy. We also note a slight decrease in cell open circuit voltage with increase in polymer regioregularity, which is due to the increase in k. Other recombination mechanisms such as trap-assisted recombination are found to be important in the lower regioregular P3HT device compounded by the reduced mobility and poor inter-chain ordering.

  18. Charge transfer state in DBP:C70 organic solar cells

    DEFF Research Database (Denmark)

    Sherafatipour, Golenaz; Benduhn, Johannes; Spoltore, Donato

    -acceptor interface via delocalized charge-transfer (CT) states, which represents an intermediate state between the exciton dissociation and recombination back to the ground state. In this work we perform the electroluminescence (EL) created by bimolecular free career recombination and sensitive external quantum...

  19. Vibrational-rotational excitation: chemical reactions of vibrationally excited molecules

    International Nuclear Information System (INIS)

    Moore, C.B.; Smith, I.W.M.

    1979-03-01

    This review considers a limited number of systems, particularly gas-phase processes. Excited states and their preparation, direct bimolecular reactions, reactions of highly excited molecules, and reactions in condensed phases are discussed. Laser-induced isotope separation applications are mentioned briefly. 109 references

  20. Kinetic equation of heterogeneous catalytic isotope exchange

    Energy Technology Data Exchange (ETDEWEB)

    Trokhimets, A I [AN Belorusskoj SSR, Minsk. Inst. Fiziko-Organicheskoj Khimii

    1979-12-01

    A kinetic equation is derived for the bimolecular isotope exchange reaction between AXsub(n)sup(*) and BXsub(m)sup(o), all atoms of element X in each molecule being equivalent. The equation can be generalized for homogeneous and heterogeneous catalytic isotope exchange.

  1. Reaction of atomic bromine with acetylene and loss rate of atmospheric acetylene due to reaction with OH, Cl, O, and Br

    Science.gov (United States)

    Payne, W. A.; Nava, D. F.; Brunning, J.; Stief, L. J.

    1986-01-01

    The first-order, diffusion, and bimolecular rate constants for the reaction Br + C2H2 yields C2H3Br are evaluated. The rate constants are measured at 210, 248, 298, and 393 K and at pressures between 15-100 torr Ar using flash photolysis combined with time-resolved detection of atomic bromine via Br resonance radiation. It is observed that the reaction is not affected by pressure or temperature and the bimolecular constant = (4.0 + or - 0.8) x 10 to the -15th cu cm/sec with an error of two standard deviations. The C2H2 + Br reaction rates are compared with reactions of C2H2 with Cl, OH, NH2, and H. The loss rates for atmospheric C2H2 for reactions with OH, Cl, O, and Br are calculated as a function of altitude.

  2. Cooper pair formation dynamics in Bi2Sr2CaCu2O8+δ

    International Nuclear Information System (INIS)

    Kaindl, R.A.; Carnahan, M.A.; Orenstein, J.; Chemla, D.S.; Oh, S.; Eckstein, J.N.

    2003-01-01

    We utilize ultrafast terahertz pulses to monitor the carrier dynamics in the high-TC superconductor Bi2Sr2CaCu2O8+delta. The temperature, density and time dependence distinctly exposes a bimolecular recombination process of quasiparticles which underlies formation of Cooper pairs

  3. A hetero retro Diels-Alder reaction in aqueous solution : A dramatic water-induced increase of the equilibrium constant and inhibition of cycloreversion

    NARCIS (Netherlands)

    Wijnen, J.W; Engberts, J.B.F.N.

    The adduct of the Diels-Alder reaction of nitrosobenzene with cyclopentadiene is not stable in solution. The equilibrium constant for the reaction depends strongly on the medium and water induces a spectacular shift to the adduct. Comparison with the bimolecular addition of nitrosobenzene to

  4. Analyzing Reaction Rates with the Distortion/Interaction-Activation Strain Model

    NARCIS (Netherlands)

    Bickelhaupt, F. Matthias; Houk, Kendall N.

    2017-01-01

    The activation strain or distortion/interaction model is a tool to analyze activation barriers that determine reaction rates. For bimolecular reactions, the activation energies are the sum of the energies to distort the reactants into geometries they have in transition states plus the interaction

  5. Exciton Formation in Disordered Semiconductors

    DEFF Research Database (Denmark)

    Klochikhin, A.; Reznitsky, A.; Permogorov, S.

    1999-01-01

    Stationary luminescence spectra of disordered solid solutions can be accounted by the model of localized excitons. Detailed analysis of the long time decay kinetics of luminescence shows that exciton formation in these systems is in great extent due to the bimolecular reaction of separated carrie...

  6. Optically Activated Exciplex Shutter/Attenuator.

    Science.gov (United States)

    radiation of a certain wavelength to excite a bi-molecular exciplex solution. The exciplex solution reacts to a range of radiation wavelengths whereas...optical elements prevent passage of radiation below and above the operative range of an exciplex solution such as anthracene and diethylaniline.

  7. Diffusion coefficients of tracers in glassy polymer systems prepared by gamma radiolysis

    International Nuclear Information System (INIS)

    Tonge, M.P.; Gilbert, R.G.

    1996-01-01

    Diffusion-controlled reactions are common in free radical polymerisation reactions, especially in glassy polymer matrices. Such reactions commonly have an important influence on the polymerisation process and final polymer properties. For example, the dominant growth-stopping event (bimolecular termination) is generally diffusion-controlled. In glassy polymer systems, where molecular mobility is very low, the chain growth mechanism (propagation) may become diffusion-controlled. At present, the mechanism for propagation in glassy polymers is poorly understood, but it is expected by the Smoluchowski expression applied to propagation to depend strongly on the diffusion coefficient of monomer. The objective of this study is to measure reliable diffusion coefficients of small tracer molecules in glassy polymers, and compare these with propagation rate coefficients in similar systems, by the prediction above. Samples were initially prepared in a sealed sampled cell containing monomer, inert diluent, and tracer dye. After irradiation for several days, complete conversion of monomer to polymer can be obtained. The diffusion coefficients for two tracer dyes have been measured as a function of weight fraction polymer glassy poly(methyl methacrylate) samples

  8. Anthracene Fluorescence Quenching by a Tetrakis (Ketocarboxamide Cavitand

    Directory of Open Access Journals (Sweden)

    Tibor Zoltan Janosi

    2014-01-01

    Full Text Available Quenching of both fluorescence lifetime and fluorescence intensity of anthracene was investigated in the presence of a newly derived tetrakis (ketocarboxamide cavitand at various concentrations. Time-correlated single photon counting method was applied for the lifetime measurements. A clear correlation between the fluorescence lifetime of anthracene as a function of cavitand concentration in dimethylformamide solution was observed. The bimolecular collisional quenching constant was derived from the decrease of lifetime. Fluorescence intensity was measured in the emission wavelength region around 400 nm as a result of excitation at 280 nm. Effective quenching was observed in the presence of the cavitand. The obtained Stern-Volmer plot displayed upward curvature. The results did not follow even extended Stern-Volmer behavior, often used to describe deviations from static bimolecular quenching. To explain our results we adopted the Smoluchowski model and obtained a reasonable estimate for the molecular radius of the cavitand in solution.

  9. Radiochemical determination of methylmercury chloride Part 1

    International Nuclear Information System (INIS)

    Stary, J.; Prasilova, J.

    1976-01-01

    The isotope exchange between methylmercury species and an excess of inorganic radiomercury in sulphuric acid medium has been used for the simple determination of methylmercury chloride down to 0.01 ppm. The determination is not influenced by the presence of a great excess of other metals, however, chlorides, bromides and iodides interfere in higher concentrations. It has been found that the isotope exchange between CH 3 HgCl and 203 HgCl 4 2- (or 203 HgCl 2 ) in 0.01-3M hydrochloric acid is extremely slow, for the bimolecular reaction the rate constant is lower than 10 -3 mol -1 s -1 at 25 deg C. The isotope exchange rate between methylmercury chloride and mercuric-nitrate 0n on 0.5M sulphuric acid is higher. The isotope exchange is a bimolecular reaction with a rate constant k=0.050+-0.004 mol -1 s -1 at 25 deg C. (T.I.)

  10. Reaction product imaging

    Energy Technology Data Exchange (ETDEWEB)

    Chandler, D.W. [Sandia National Laboratories, Livermore, CA (United States)

    1993-12-01

    Over the past few years the author has investigated the photochemistry of small molecules using the photofragment imaging technique. Bond energies, spectroscopy of radicals, dissociation dynamics and branching ratios are examples of information obtained by this technique. Along with extending the technique to the study of bimolecular reactions, efforts to make the technique as quantitative as possible have been the focus of the research effort. To this end, the author has measured the bond energy of the C-H bond in acetylene, branching ratios in the dissociation of HI, the energetics of CH{sub 3}Br, CD{sub 3}Br, C{sub 2}H{sub 5}Br and C{sub 2}H{sub 5}OBr dissociation, and the alignment of the CD{sub 3} fragment from CD{sub 3}I photolysis. In an effort to extend the technique to bimolecular reactions the author has studied the reaction of H with HI and the isotopic exchange reaction between H and D{sub 2}.

  11. Photo-induced cooperative covalent-bond switching in amorphous arsenic selenide

    Energy Technology Data Exchange (ETDEWEB)

    Shpotyuk, O [Lviv Scientific Research Institute of Materials of SRC ' Carat' , 202, Stryjska str., Lviv, UA-290031 (Ukraine); Balitska, V [Lviv Scientific Research Institute of Materials of SRC ' Carat' , 202, Stryjska str., Lviv, UA-290031 (Ukraine); Filipecki, J [Institute of Physics of Jan Dlugosz University, 13/15, Al. Armii Krajowej, Czestochowa, PL-42201 (Poland)

    2005-01-01

    A microstructural mechanism of photoinduced transformations in amorphous arsenic selenide films was studied with IR Fourier-spectroscopy technique in 300-100 cm{sup -1} region. It was shown that stage of irreversible photostructural changes was connected with cooperative process of coordination defect formation accompanied by homopolar chemical bonds switching in heteropolar ones. On the contrary, reversible photoinduced effects were caused by heteropolar chemical bonds switching in homopolar ones, as well as additional channel of bridge heteropolar bonds switching in short-layer ones. The both processes were associated with formation of anomalously coordinated defect pairs and accompanying atomic displacements at the level of medium-range ordering. The developed mathematical simulation procedure testified in a favour of defect-related origin of the reversible photo-thermallyinduced transformations, since their kinetics corresponded to known stretched-exponential dependence, tending to bimolecular behaviour rather then to single-exponential one.

  12. Advanced Oxidation Degradation of Diclofenac

    Energy Technology Data Exchange (ETDEWEB)

    Cooper, William J., E-mail: wcooper@uci.edu [Urban Water Research Center, Department of Civil and Environmental Engineering, University of California, Irvine, CA 92697 (United States); Song Weihua, E-mail: wsong@fudan.edu.cn [Department of Environmental Science & Engineering, Fudan University, Shanghai 200433 (China)

    2012-07-01

    Advanced oxidation/reduction processes (AO/RPs), utilize free radical reactions to directly degrade chemical contaminants as an alternative to traditional water treatment. This study reports the absolute rate constants for reaction of diclofenac sodium and the model compound (2, 6-dichloraniline) with the two major AO/RP radicals; the hydroxyl radical (•OH) and hydrated electron (e{sup -}{sub aq}). The bimolecular reaction rate constants (M{sup -1} s{sup -1}) for diclofenac for •OH was (9.29 ± 0.11) x 10{sup 9}, and, for e- aq was (1.53 ± 0.03) x10{sup 9}. Preliminary degradation mechanisms are suggested based on product analysis using {sup 60}Co γ-irradiation and LC-MS for reaction by-product identification. The toxicity of products was evaluated using the Vibrio fischeri luminescent bacteria method. (author)

  13. The Atmospheric Oxidation of Volatile Organic Compounds Through Hydrogen Shift Reactions

    DEFF Research Database (Denmark)

    Knap, Hasse Christian

    a radical is denoted as a H-shift reaction. Quantum chemical calculations were carried out to investigate the potential energy surface of the H-shift reactions and the subsequent decomposition pathways. The transition state theory including the Eckart quantum tunneling correction have been used to calculate...... the reaction rate constants of the H-shift reactions. The autoxidation of volatile organic compounds is an important oxidation mechanism that produces secondary organic aerosols (SOA) and recycles hydroxyl (OH) radicals. The autoxidation cycle produces a second generation peroxy radical (OOQOOH) through...... a series of H-shift reactions and O2 attachments. I have investigated the H-shift reactions in two OOQOOH radicals (hydroperoxy peroxy radicals and hydroperoxy acyl peroxy radicals). The H-shift reaction rate constants have been compared with the bimolecular reaction rate constants of the peroxy radicals...

  14. The radiochemistry of [{sup 18} F]-FDG: the first experience in Mexico; La radioquimica del [{sup 18} F]-FDG: la primera experiencia en Mexico

    Energy Technology Data Exchange (ETDEWEB)

    Lopez D, F A [Unidad PET-Ciclotron, Facultad de Medicina, UNAM, Av. Universidad 3000, Ciudad Universitaria, Coyoacan, 04500 Mexico, D. F. (Mexico)

    2004-07-01

    The present work describes the more used method for the synthesis of 2 - [{sup 18} F] - fluorine-2-deoxy-D-glucose that is the more used radiopharmaceutical in the nuclear medicine in the cancer diagnostic. The process consists on two chemical reactions: i) [{sup 18} F{sup -}] - nucleophilic radio fluorination and i i) a hydrolysis catalyzed by acid. The first reaction incorporates to the [{sup 18} F]- fluorine labelled inside the organic precursor 1,3,4,6-tetra- O -acetil-2- O-trifluoromethanesulfonyl- {beta}-D-mannopyranose (triflate of mannose). The mechanism of this reaction is a bimolecular nucleophilic substitution (SN{sub 2}) with the ion [{sup 18} F{sup -}] - fluoride; in the second reaction, the hydrolysis of those protective acetyl groups generate the hydroxyl groups free of the [{sup 18} F]-FDG. The process includes an azeotropic distillation and several purification steps. (Author)

  15. Time resolved photoluminescence studies of long lived emissive specie in F8BT:PFB blends

    Science.gov (United States)

    Gélinas, Simon; Howard, Ian; Friend, Richard; Silva, Carlos

    2009-03-01

    Type-II heterojunctions play a crucial role in organic optoelectronic devices. We use donor-acceptor polyfluorene blends as a model system to understand excited-state dynamics at heterojunctions. These interfacial excitations are intrachain singlet and triplet excitons, geminate polaron pairs, and exciplexes (interfacial charge-transfer excitons). Time-resolved photoluminescence (PL) spectra were taken at 10,and room temperature to investigate the interconversion dynamics of these species. We observe delayed PL with sub-linear excitation fluence dependence. This implies that delayed singlet exciton generation involves a bimolecular annihilation mechanism. By means of kinetic modeling, we propose triplet-triplet exciton annihilation as a regeneration route to singlet excitons, and subsequently to exciplexes. This points to a significant (<15,%) yield of triplet excitons after interfacial charge separation, and to the central role of these species on the interfacial dynamics.

  16. A solution-processed binary cathode interfacial layer facilitates electron extraction for inverted polymer solar cells.

    Science.gov (United States)

    Zhang, Xinyuan; Li, Zhiqi; Liu, Chunyu; Guo, Jiaxin; Shen, Liang; Guo, Wenbin

    2018-03-15

    The charge transfer and separation are significantly affected by the electron properties of the interface between the electron-donor layer and the carrier-transporting layer in polymer solar cells (PSCs). In this study, we investigate the electron extraction mechanism of PSCs with a low temperature solution-processed ZnO/PEI as electron transport layer. The incorporation of PEI layer can decrease the work function of ZnO and reduce interfacial barrier, which facilitates electron extraction and suppresses bimolecular recombination, leading to a significant performance enhancement. Furthermore, PEI layer can induce phase separation and passivite inorganic surface trap states as well as shift the interfacial energy offset between metal oxide and organic materials. This work offers a simple and effective way to improve the charge transporting property of organic photovoltaic devices. Copyright © 2017 Elsevier Inc. All rights reserved.

  17. Impact of the electron-transport layer on the performance of solution-processed small-molecule organic solar cells.

    Science.gov (United States)

    Long, Guankui; Wan, Xiangjian; Kan, Bin; Hu, Zhicheng; Yang, Xuan; Zhang, Yi; Zhang, Mingtao; Wu, Hongbing; Huang, Fei; Su, Shijian; Cao, Yong; Chen, Yongsheng

    2014-08-01

    Although the performance of polymer solar cells has been improved significantly recently through careful optimization with different interlayers for the same materials, more improvement is needed in this respect for small-molecule-based solar cells, particularly for the electron-transport layers (ETLs). In this work, three different solution-processed ETLs, PFN, ZnO nanoparticles, and LiF, were investigated and compared in the performance of small-molecule-based devices, and power conversion efficiencies (PCEs) of 8.32, 7.30, and 7.38% were achieved, respectively. The mechanism for the ETL-induced enhancement has been studied, and different ETLs have a significantly different impact on the device performance. The clearly improved performance of PFN is attributed to the combination of reduced bimolecular recombination and increased effective photon absorption in the active layer. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. High mechanical advantage design of six-bar Stephenson mechanism for servo mechanical presses

    Directory of Open Access Journals (Sweden)

    Jianguo Hu

    2016-06-01

    Full Text Available This article proposed a two-phase design scheme of Stephenson six-bar working mechanisms for servo mechanical presses with high mechanical advantage. In the qualitative design phase, first, a Stephenson six-bar mechanism with a slide was derived from Stephenson six-bar kinematic chains. Second, based on the instant center analysis method, the relationship between mechanical advantage and some special instant centers was founded, and accordingly a primary mechanism configuration with high mechanical advantage was designed qualitatively. Then, a parameterized prototype model was established, and the influences of design parameters toward slide kinematical characteristics were analyzed. In the quantitative design phase, a multi-objective optimization model, aiming at high mechanical advantage and dwelling characteristics, was built, and a case design was done to find optimal dimensions. Finally, simulations based on the software ADAMS were conducted to compare the transmission characteristics of the optimized working mechanism with that of slide-crank mechanism and symmetrical toggle mechanism, and an experimental press was made to validate the design scheme. The simulation and experiment results show that, compared with general working mechanisms, the Stephenson six-bar working mechanism has higher mechanical advantage and better dwelling characteristics, reducing capacities and costs of servo motors effectively.

  19. The action of polyene antibiotics on lipid bilayer membranes in the presence of several cations and anions

    NARCIS (Netherlands)

    Zutphen, H. van; Demel, R.A.; Norman, A.W.; Deenen, L.L.M. van

    1971-01-01

    1. 1. Filipin complex, filipin II, filipin III, nystatin, etruscomycin, and pimaricin at concentrations of 10−5 M were able to disrupt bimolecular lipid films containing lecithin and cholesterol in a 1:1 molar ratio. 2. 2. The above antibiotics were not able to disrupt lecithin bilayer

  20. Screening a cDNA library for protein-protein interactions directly in planta

    Czech Academy of Sciences Publication Activity Database

    Lee, L.-Y.; Wu, F.-H.; Hsu, Ch.-T.; Shen, S.-Ch.; Yeh, H.-Y.; Liao, D.-Ch.; Fang, M.-J.; Liu, N.-T.; Yen, Y.-Ch.; Dokládal, Ladislav; Sýkorová, Eva; Gelvin, S.B.; Lin, Ch.-S.

    2012-01-01

    Roč. 24, č. 5 (2012), s. 1746-1759 ISSN 1040-4651 R&D Projects: GA AV ČR(CZ) IAA500040801 Institutional research plan: CEZ:AV0Z50040702 Keywords : bimolecular fluorescence complementation * telomerase-binding-protein * transformation Subject RIV: BO - Biophysics Impact factor: 9.251, year: 2012

  1. Energy transfer in diatom/diatom molecular collisions

    International Nuclear Information System (INIS)

    Sohlberg, K.W.

    1992-01-01

    In a collision of two molecules, the translational energy of the collision may be redistributed into internal energy of rotation, vibration, or electron motion, in one or both of the colliding partners. In addition, internal energy in one or more of these modes may be open-quotes quenchedclose quotes into translation, leading to a superelastic collision. Such energy transfer may take place by a number of mechanisms. This energy transfer is of fundamental importance in understanding chemical reaction dynamics. Nearly all chemical reactions take place through a bimolecular collision process (or multiple bimolecular collisions) and the quantum state specificity of the reaction can have a major role in determining the kinetics of the reaction, In particular, the author has investigated vibrational energy transfer in collisions between two diatomic molecules. In addition to serving as models for all molecular collision process, gas phase collisions of these species are ubiquitous in atmospheric phenomena which are of critical importance in answering the current questions about the human induced degradation of the earth's atmospheric. Classical trajectory methods have been used to explore the excitation of vibrations in gas-phase collisions of the nitrogen molecular ion with its parent molecule. The near symmetry of the reactants is shown to result in a high probability that the two molecules are excited by an equal amount of energy. This provides a possible explanation of the molecular beam measurements which show that the total number of vibrational energy quanta excited in the collision is, with a high probability that the two molecules are excited by an equal amount of energy. This provides a possible explanation of the molecular beam measurements which show that the total number of vibrational energy quanta excited in the collision is, with a high probability, even

  2. Quantum Mechanics/Molecular Mechanics Study of the Sialyltransferase Reaction Mechanism.

    Science.gov (United States)

    Hamada, Yojiro; Kanematsu, Yusuke; Tachikawa, Masanori

    2016-10-11

    The sialyltransferase is an enzyme that transfers the sialic acid moiety from cytidine 5'-monophospho-N-acetyl-neuraminic acid (CMP-NeuAc) to the terminal position of glycans. To elucidate the catalytic mechanism of sialyltransferase, we explored the potential energy surface along the sialic acid transfer reaction coordinates by the hybrid quantum mechanics/molecular mechanics method on the basis of the crystal structure of sialyltransferase CstII. Our calculation demonstrated that CstII employed an S N 1-like reaction mechanism via the formation of a short-lived oxocarbenium ion intermediate. The computational barrier height was 19.5 kcal/mol, which reasonably corresponded with the experimental reaction rate. We also found that two tyrosine residues (Tyr156 and Tyr162) played a vital role in stabilizing the intermediate and the transition states by quantum mechanical interaction with CMP.

  3. Mechanics without mechanisms

    Science.gov (United States)

    Eisenthal, Joshua

    2018-05-01

    At the time of Heinrich Hertz's premature death in 1894, he was regarded as one of the leading scientists of his generation. However, the posthumous publication of his treatise in the foundations of physics, Principles of Mechanics, presents a curious historical situation. Although Hertz's book was widely praised and admired, it was also met with a general sense of dissatisfaction. Almost all of Hertz's contemporaries criticized Principles for the lack of any plausible way to construct a mechanism from the "hidden masses" that are particularly characteristic of Hertz's framework. This issue seemed especially glaring given the expectation that Hertz's work might lead to a model of the underlying workings of the ether. In this paper I seek an explanation for why Hertz seemed so unperturbed by the difficulties of constructing such a mechanism. In arriving at this explanation, I explore how the development of Hertz's image-theory of representation framed the project of Principles. The image-theory brings with it an austere view of the "essential content" of mechanics, only requiring a kind of structural isomorphism between symbolic representations and target phenomena. I argue that bringing this into view makes clear why Hertz felt no need to work out the kinds of mechanisms that many of his readers looked for. Furthermore, I argue that a crucial role of Hertz's hypothesis of hidden masses has been widely overlooked. Far from acting as a proposal for the underlying structure of the ether, I show that Hertz's hypothesis ruled out knowledge of such underlying structure.

  4. Investigation of Nonholonomic Mechanics, Vakonomic Mechanics ...

    African Journals Online (AJOL)

    In this article, methods of modeling dynamic systems namely, Nonholonomic mechanics, Vakonomic mechanics and Chetaev methods for constrained dynamic system are investigated. The fact that Vakonomic mechanics gives a different motion equation to the other methods is verified using a particular example. It is shown ...

  5. Fracture Mechanics

    International Nuclear Information System (INIS)

    Jang, Dong Il; Jeong, Gyeong Seop; Han, Min Gu

    1992-08-01

    This book introduces basic theory and analytical solution of fracture mechanics, linear fracture mechanics, non-linear fracture mechanics, dynamic fracture mechanics, environmental fracture and fatigue fracture, application on design fracture mechanics, application on analysis of structural safety, engineering approach method on fracture mechanics, stochastic fracture mechanics, numerical analysis code and fracture toughness test and fracture toughness data. It gives descriptions of fracture mechanics to theory and analysis from application of engineering.

  6. Functional requirements of AID's higher order structures and their interaction with RNA-binding proteins.

    Science.gov (United States)

    Mondal, Samiran; Begum, Nasim A; Hu, Wenjun; Honjo, Tasuku

    2016-03-15

    Activation-induced cytidine deaminase (AID) is essential for the somatic hypermutation (SHM) and class-switch recombination (CSR) of Ig genes. Although both the N and C termini of AID have unique functions in DNA cleavage and recombination, respectively, during SHM and CSR, their molecular mechanisms are poorly understood. Using a bimolecular fluorescence complementation (BiFC) assay combined with glycerol gradient fractionation, we revealed that the AID C terminus is required for a stable dimer formation. Furthermore, AID monomers and dimers form complexes with distinct heterogeneous nuclear ribonucleoproteins (hnRNPs). AID monomers associate with DNA cleavage cofactor hnRNP K whereas AID dimers associate with recombination cofactors hnRNP L, hnRNP U, and Serpine mRNA-binding protein 1. All of these AID/ribonucleoprotein associations are RNA-dependent. We propose that AID's structure-specific cofactor complex formations differentially contribute to its DNA-cleavage and recombination functions.

  7. Long Lived Photoexcitation Dynamics in π-Conjugated Polymer/PbS Quantum Dot Blended Films for Photovoltaic Application

    Directory of Open Access Journals (Sweden)

    Ruizhi Wang

    2017-08-01

    Full Text Available We used continuous wave photoinduced absorption (PIA spectroscopy to investigate long-lived polarons in a blend of PbS quantum dot and regio-regular poly (3-hexylthiophene (RR-P3HT. The charge transfer from RR-P3HT to PbS as well as from PbS to RR-P3HT were observed after changing the capping ligand of PbS from a long chain molecular to a short one. Therefore, PbS could be used to extend the working spectral range in hybrid solar cells with a proper capping ligand. However, we found that the recombination mechanism in the millisecond time region is dominated by the trap/defects in blended films, while it improves to a bimolecular recombination partially after ligand exchange. Our results suggest that passivating traps of nanocrystals by improving surface ligands will be crucial for relevant solar cell applications.

  8. The Mechanics of Mechanical Watches and Clocks

    CERN Document Server

    Du, Ruxu

    2013-01-01

    "The Mechanics of Mechanical Watches and Clocks" presents historical views and mathematical models of mechanical watches and clocks. Although now over six hundred years old, mechanical watches and clocks are still popular luxury items that fascinate many people around the world. However few have examined the theory of how they work as presented in this book. The illustrations and computer animations are unique and have never been published before. It will be of significant interest to researchers in mechanical engineering, watchmakers and clockmakers, as well as people who have an engineering background and are interested in mechanical watches and clocks. It will also inspire people in other fields of science and technology, such as mechanical engineering and electronics engineering, to advance their designs. Professor Ruxu Du works at the Chinese University of Hong Kong, China. Assistant Professor Longhan Xie works at the South China University of Technology, China.

  9. Catalytic properties and dynamic behaviour of uranium complexes

    International Nuclear Information System (INIS)

    Le Marechal, J.F.

    1986-01-01

    The catalytic properties of organometallic uranium III and IV compounds in solution as well as reaction mechanisms are studied. The structure in solution of CpUCl 3 L 2 (L=THF, HMPA, OPPh 3 , OP(OR) 3 ) is investigated. When L=HMPA, the complex exists in two isomers in equilibrium with the L ligands either in trans or mer-cis configuration. The isomerization (Ea=92 kJ mol -1 ) as well as the bimolecular exchange with an outer sphere ligand L are observable in 1 H and 31 P NMR, and quantified with the spin saturation transfer technique in several solvents and at different temperatures between 230 and 330 K. This property is extended to other ligands. The compound U(AlH 4 ) 3 is synthetized. This compound catalyses the hydroalumination of olefins by LiAlH 4 with a very good anti-Markovnikov regioselectivity. A simple mechanism for this reaction is suggested. The reactions of the organoaluminates products with several reactants (D 2 O, I 2 , CH 2 O, Allyl-Br...) has been shown to be a powerful synthetic tool. Some specific alkenes and alkynes exhibit an interesting behaviour as dimerization or β-alkyl elimination which is easily interpreted by our mechanism [fr

  10. The importance of fullerene percolation in the mixed regions of polymer-fullerene bulk heterojunction solar cells

    KAUST Repository

    Bartelt, Jonathan A.; Beiley, Zach M.; Hoke, Eric T.; Mateker, William R.; Douglas, Jessica D.; Collins, Brian A.; Tumbleston, John R.; Graham, Kenneth; Amassian, Aram; Ade, Harald W.; Frechet, Jean; Toney, Michael F.; McGehee, Michael D.

    2012-01-01

    Most optimized donor-acceptor (D-A) polymer bulk heterojunction (BHJ) solar cells have active layers too thin to absorb greater than - 80% of incident photons with energies above the polymer's band gap. If the thickness of these devices could be increased without sacrifi cing internal quantum effi ciency, the device power conversion effi ciency (PCE) could be signifi cantly enhanced. We examine the device characteristics of BHJ solar cells based on poly(di(2- ethylhexyloxy)benzo[1,2- b :4,5- b ' ]dithiophene- co -octylthieno[3,4- c ]pyrrole-4,6- dione) (PBDTTPD) and [6,6]-phenyl-C 61 -butyric acid methyl ester (PCBM) with 7.3% PCE and fi nd that bimolecular recombination limits the active layer thickness of these devices. Thermal annealing does not mitigate these bimolecular recombination losses and drastically decreases the PCE of PBDTTPD BHJ solar cells. We characterize the morphology of these BHJs before and after thermal annealing and determine that thermal annealing drastically reduces the concentration of PCBM in the mixed regions, which consist of PCBM dispersed in the amorphous portions of PBDTTPD. Decreasing the concentration of PCBM may reduce the number of percolating electron transport pathways within these mixed regions and create morphological electron traps that enhance charge-carrier recombination and limit device quantum effi ciency. These fi ndings suggest that (i) the concentration of PCBM in the mixed regions of polymer BHJs must be above the PCBM percolation threshold in order to attain high solar cell internal quantum effi ciency, and (ii) novel processing techniques, which improve polymer hole mobility while maintaining PCBM percolation within the mixed regions, should be developed in order to limit bimolecular recombination losses in optically thick devices and maximize the PCE of polymer BHJ solar cells. © 2013 WILEY-VCH Verlag GmbH and Co. © 2013 WILEY-VCH Verlag GmbH & Co.

  11. The importance of fullerene percolation in the mixed regions of polymer-fullerene bulk heterojunction solar cells

    KAUST Repository

    Bartelt, Jonathan A.

    2012-10-26

    Most optimized donor-acceptor (D-A) polymer bulk heterojunction (BHJ) solar cells have active layers too thin to absorb greater than - 80% of incident photons with energies above the polymer\\'s band gap. If the thickness of these devices could be increased without sacrifi cing internal quantum effi ciency, the device power conversion effi ciency (PCE) could be signifi cantly enhanced. We examine the device characteristics of BHJ solar cells based on poly(di(2- ethylhexyloxy)benzo[1,2- b :4,5- b \\' ]dithiophene- co -octylthieno[3,4- c ]pyrrole-4,6- dione) (PBDTTPD) and [6,6]-phenyl-C 61 -butyric acid methyl ester (PCBM) with 7.3% PCE and fi nd that bimolecular recombination limits the active layer thickness of these devices. Thermal annealing does not mitigate these bimolecular recombination losses and drastically decreases the PCE of PBDTTPD BHJ solar cells. We characterize the morphology of these BHJs before and after thermal annealing and determine that thermal annealing drastically reduces the concentration of PCBM in the mixed regions, which consist of PCBM dispersed in the amorphous portions of PBDTTPD. Decreasing the concentration of PCBM may reduce the number of percolating electron transport pathways within these mixed regions and create morphological electron traps that enhance charge-carrier recombination and limit device quantum effi ciency. These fi ndings suggest that (i) the concentration of PCBM in the mixed regions of polymer BHJs must be above the PCBM percolation threshold in order to attain high solar cell internal quantum effi ciency, and (ii) novel processing techniques, which improve polymer hole mobility while maintaining PCBM percolation within the mixed regions, should be developed in order to limit bimolecular recombination losses in optically thick devices and maximize the PCE of polymer BHJ solar cells. © 2013 WILEY-VCH Verlag GmbH and Co. © 2013 WILEY-VCH Verlag GmbH & Co.

  12. Mechanisms Design

    DEFF Research Database (Denmark)

    Restrepo-Giraldo, John Dairo

    2006-01-01

    Most products and machines involve some kind of controlled movement. From window casements to DVD players, from harbor cranes to the shears to prune your garden, all these machines require mechanisms to move. This course intends to provide the analytical and conceptual tools to design such mechan......Most products and machines involve some kind of controlled movement. From window casements to DVD players, from harbor cranes to the shears to prune your garden, all these machines require mechanisms to move. This course intends to provide the analytical and conceptual tools to design...... using criteria such as size, performance parameters, operation environment, etc. Content: Understanding Mechanisms Design (2 weeks) Definitions, mechanisms representations, kinematic diagrams, the four bar linkage, mobility, applications of mechanisms, types of mechanisms, special mechanisms, the design......: equations for various mechanisms. At the end of this module you will be able to analyze existing mechanisms and to describe their movement. Designing mechanisms (7 weeks) Type synthesis and dimensional synthesis, function generation, path generation, three precision points in multi-loop mechanisms...

  13. Reactions of OH Radicals with Tris (1,10-Phenanthroline) Iron (II) Studied by Pulse Radiolysis

    DEFF Research Database (Denmark)

    Siekierska Floryan, E.; Pagsberg, Palle Bjørn

    1976-01-01

    The reaction of OH radicals with aqueous tris(1,10-phenanthroline)iron(II) leads to the formation of an adduct, which exhibits a broad absorption band at rmpH = 6, λmax = 460 nm, and epsilon (Porson)460 = 6700 (molar, decadic, 1 mol−1 cm−1). The rate of formation of the adduct is first order...... in complex concentration with a bimolecular rate constant Image independent of pH in the range pH 3–11. The adduct decays by mixed-order kinetics, but at 310 nm a second-order formation of a decay product can be directly observed. The reaction of OH radicals with aqueous 1,10-phenanthroline leads also...... to the formation of an adduct which absorbs in the whole visible region with a maximum at 425 nm and ε425 = 2612 (molar, decadic, 1 mol−1 cm−1) in neutral solution. The adduct exhibits a red shift in acidic and alkaline media. The formation is first order in 1,10-phenanthroline with a bimolecular rate constant...

  14. Are Nonadiabatic Reaction Dynamics the Key to Novel Organosilicon Molecules? The Silicon (Si(3P))-Dimethylacetylene (C4H6(X1A1g)) System as a Case Study.

    Science.gov (United States)

    Thomas, Aaron M; Dangi, Beni B; Yang, Tao; Kaiser, Ralf I; Lin, Lin; Chou, Tzu-Jung; Chang, Agnes H H

    2018-06-06

    The bimolecular gas phase reaction of ground-state silicon (Si; 3 P) with dimethylacetylene (C 4 H 6 ; X 1 A 1g ) was investigated under single collision conditions in a crossed molecular beams machine. Merged with electronic structure calculations, the data propose nonadiabatic reaction dynamics leading to the formation of singlet SiC 4 H 4 isomer(s) and molecular hydrogen (H 2 ) via indirect scattering dynamics along with intersystem crossing (ISC) from the triplet to the singlet surface. The reaction may lead to distinct energetically accessible singlet SiC 4 H 4 isomers ( 1 p8- 1 p24) in overall exoergic reaction(s) (-107 -20 +12 kJ mol -1 ). All feasible reaction products are either cyclic, carry carbene analogous silylene moieties, or carry C-Si-H or C-Si-C bonds that would require extensive isomerization from the initial collision complex(es) to the fragmenting singlet intermediate(s). The present study demonstrates the first successful crossed beams study of an exoergic reaction channel arising from bimolecular collisions of silicon, Si( 3 P), with a hydrocarbon molecule.

  15. Continuum mechanics

    CERN Document Server

    Spencer, A J M

    2004-01-01

    The mechanics of fluids and the mechanics of solids represent the two major areas of physics and applied mathematics that meet in continuum mechanics, a field that forms the foundation of civil and mechanical engineering. This unified approach to the teaching of fluid and solid mechanics focuses on the general mechanical principles that apply to all materials. Students who have familiarized themselves with the basic principles can go on to specialize in any of the different branches of continuum mechanics. This text opens with introductory chapters on matrix algebra, vectors and Cartesian ten

  16. Topological Higgs mechanism with ordinary Higgs mechanism

    International Nuclear Information System (INIS)

    Oda Ichiro; Yahikozawa Shigeaki.

    1989-12-01

    Topological Higgs mechanism in higher dimensions is analyzed when ordinary Higgs potential exists. It is shown that if one-form B-field becomes massive by the ordinary Higgs mechanism, another D-2 form C-field also becomes massive through topological term in addition to the topological mass generation by the topological Higgs mechanism. Moreover we investigate this mechanism in three dimensional theories, that is to say, Chern-Simons theory and more general theory. (author). 10 refs

  17. Analytical mechanics for relativity and quantum mechanics

    CERN Document Server

    Johns, Oliver Davis

    2011-01-01

    Analytical Mechanics for Relativity and Quantum Mechanics is an innovative and mathematically sound treatment of the foundations of analytical mechanics and the relation of classical mechanics to relativity and quantum theory. It is intended for use at the introductory graduate level. A distinguishing feature of the book is its integration of special relativity into teaching of classical mechanics. After a thorough review of the traditional theory, Part II of the book introduces extended Lagrangian and Hamiltonian methods that treat time as a transformable coordinate rather than the fixed parameter of Newtonian physics. Advanced topics such as covariant Langrangians and Hamiltonians, canonical transformations, and Hamilton-Jacobi methods are simplified by the use of this extended theory. And the definition of canonical transformation no longer excludes the Lorenz transformation of special relativity. This is also a book for those who study analytical mechanics to prepare for a critical exploration of quantum...

  18. 2-Aminopyrimidine-3,3,3-triphenylpropanoic acid (1/1).

    Science.gov (United States)

    Serafin, Mateusz F; Wheeler, Kraig A

    2007-11-01

    The title bimolecular compound, C(4)H(5)N(3).C(21)H(18)O(2), constructed from 2-aminopyrimidine and 3,3,3-triphenylpropanoic acid, forms a tetramolecular hydrogen-bonded motif via O-H...N, N-H...O and N-H...N contacts. This aggregate organizes to give crystal-packing motifs with hydrophilic and hydrophobic regions.

  19. Multilevel regulation of an alpha-arrestin by glucose depletion controls hexose transporter endocytosis

    Czech Academy of Sciences Publication Activity Database

    Hovsepian, J.; Defenouillere, Q.; Albanese, V.; Váchová, Libuše; Garcia, C.; Palková, Zdena; Léon, S.

    2017-01-01

    Roč. 216, č. 6 (2017), s. 1811-1831 ISSN 0021-9525 R&D Projects: GA MŠk(CZ) LQ1604; GA ČR(CZ) GA15-08225S Institutional support: RVO:61388971 Keywords : YEAST SACCHAROMYCES-CEREVISIAE * BIMOLECULAR FLUORESCENCE COMPLEMENTATION * GAP1 PERMEASE UBIQUITYLATION Subject RIV: EE - Microbiology, Virology OBOR OECD: Microbiology Impact factor: 7.955, year: 2016

  20. Mechanical stop mechanism for overcoming MEMS fabrication tolerances

    International Nuclear Information System (INIS)

    Hussein, Hussein; Bourbon, Gilles; Le Moal, Patrice; Lutz, Philippe; Haddab, Yassine

    2017-01-01

    A mechanical stop mechanism is developed in order to compensate MEMS fabrication tolerances in discrete positioning. The mechanical stop mechanism is designed to be implemented on SOI wafers using a common DRIE etching process. The various fabrication tolerances obtained due to the etching process are presented and discussed in the paper. The principle and design of the mechanism are then presented. Finally, experiments on microfabricated positioning prototypes show accurate steps unaffected by the fabrication tolerances. (technical note)

  1. Voltage-Gated Transport of Nanoparticles across Free-Standing All-Carbon-Nanotube-Based Hollow-Fiber Membranes.

    Science.gov (United States)

    Wei, Gaoliang; Quan, Xie; Chen, Shuo; Fan, Xinfei; Yu, Hongtao; Zhao, Huimin

    2015-07-15

    Understanding the mechanism underlying controllable transmembrane transport observed in biological membranes benefits the development of next-generation separation membranes for a variety of important applications. In this work, on the basis of common structural features of cell membranes, a very simple biomimetic membrane system exhibiting gated transmembrane performance has been constructed using all-carbon-nanotube (CNT)-based hollow-fiber membranes. The conductive CNT membranes with hydrophobic pore channels can be positively or negatively charged and are consequently capable of regulating the transport of nanoparticles across their pore channels by their "opening" or "closing". The switch between penetration and rejection of nanoparticles through/by CNT membranes is of high efficiency and especially allows dynamic control. The underlying mechanism is that CNT pore channels with different polarities can prompt or prevent the formation of their noncovalent interactions with charged nanoparticles, resulting in their rejection or penetration by/through the CNT membranes. The theory about noncovalent interactions and charged pore channels may provide new insight into understanding the complicated ionically and bimolecularly gated transport across cell membranes and can contribute to many other important applications beyond the water purification and resource recovery demonstrated in this study.

  2. The potential of medium-pore zeolites for improved propene yields from catalytic cracking

    Energy Technology Data Exchange (ETDEWEB)

    Bager, F.; Salas, N.; Ernst, S. [Technische Univ. Kaiserslautern (Germany). Dept. of Chemistry, Chemical Technology

    2011-07-01

    The medium-pore zeolites ZSM-5 (MFI), ZSM-22 (TON), ZSM-23 (MTT), and EU-1 (EUO) were synthesized under hydrothermal conditions and modified by ion exchange to obtain the Broensted-acid forms. The activity and selectivity of these catalysts in catalytic cracking of a model compound, viz. n-octane, was studied in a fixed-bed flow-type reactor. The catalytic results clearly reflect the differences in the pore architectures of the tested zeolites on n-octane conversion and on the product selectivities. Over the zeolites with one-dimensional pore systems and without large intracrystalline cavities, a remarkable increase of the contribution of the monomolecular cracking mechanism could be observed as compared to the standard catalyst zeolite ZSM-5. This is indicated by a high selectivity for unsaturated products and, hence, increasing yields of propene. Large cavities in the pore system, viz. in the case of zeolite EU-1, increase the conversion in particular at lower temperatures. However, the large cavities also favor the formation of large transition states required for the classical bimolecular cracking mechanism, resulting in decreased selectivities for unsaturated products, increased selectivities for aromatics formation and faster deactivation. (orig.)

  3. Photodissociation of ultracold diatomic strontium molecules with quantum state control.

    Science.gov (United States)

    McDonald, M; McGuyer, B H; Apfelbeck, F; Lee, C-H; Majewska, I; Moszynski, R; Zelevinsky, T

    2016-07-07

    Chemical reactions at ultracold temperatures are expected to be dominated by quantum mechanical effects. Although progress towards ultracold chemistry has been made through atomic photoassociation, Feshbach resonances and bimolecular collisions, these approaches have been limited by imperfect quantum state selectivity. In particular, attaining complete control of the ground or excited continuum quantum states has remained a challenge. Here we achieve this control using photodissociation, an approach that encodes a wealth of information in the angular distribution of outgoing fragments. By photodissociating ultracold (88)Sr2 molecules with full control of the low-energy continuum, we access the quantum regime of ultracold chemistry, observing resonant and nonresonant barrier tunnelling, matter-wave interference of reaction products and forbidden reaction pathways. Our results illustrate the failure of the traditional quasiclassical model of photodissociation and instead are accurately described by a quantum mechanical model. The experimental ability to produce well-defined quantum continuum states at low energies will enable high-precision studies of long-range molecular potentials for which accurate quantum chemistry models are unavailable, and may serve as a source of entangled states and coherent matter waves for a wide range of experiments in quantum optics.

  4. Arabidopsis Intracellular NHX-Type Sodium-Proton Antiporters are Required for Seed Storage Protein Processing.

    Science.gov (United States)

    Ashnest, Joanne R; Huynh, Dung L; Dragwidge, Jonathan M; Ford, Brett A; Gendall, Anthony R

    2015-11-01

    The Arabidopsis intracellular sodium-proton exchanger (NHX) proteins AtNHX5 and AtNHX6 have a well-documented role in plant development, and have been used to improve salt tolerance in a variety of species. Despite evidence that intracellular NHX proteins are important in vacuolar trafficking, the mechanism of this role is poorly understood. Here we show that NHX5 and NHX6 are necessary for processing of the predominant seed storage proteins, and also influence the processing and activity of a vacuolar processing enzyme. Furthermore, we show by yeast two-hybrid and bimolecular fluorescence complementation (BiFC) technology that the C-terminal tail of NHX6 interacts with a component of Retromer, another component of the cell sorting machinery, and that this tail is critical for NHX6 activity. These findings demonstrate that NHX5 and NHX6 are important in processing and activity of vacuolar cargo, and suggest a mechanism by which NHX intracellular (IC)-II antiporters may be involved in subcellular trafficking. © The Author 2015. Published by Oxford University Press on behalf of Japanese Society of Plant Physiologists. All rights reserved. For permissions, please email: journals.permissions@oup.com.

  5. Puzzling Mechanisms

    Science.gov (United States)

    van Deventer, M. Oskar

    2009-01-01

    The basis of a good mechanical puzzle is often a puzzling mechanism. This article will introduce some new puzzling mechanisms, like two knots that engage like gears, a chain whose links can be interchanged, and flat gears that do not come apart. It illustrates how puzzling mechanisms can be transformed into real mechanical puzzles, e.g., by…

  6. Classical Mechanics as Nonlinear Quantum Mechanics

    International Nuclear Information System (INIS)

    Nikolic, Hrvoje

    2007-01-01

    All measurable predictions of classical mechanics can be reproduced from a quantum-like interpretation of a nonlinear Schroedinger equation. The key observation leading to classical physics is the fact that a wave function that satisfies a linear equation is real and positive, rather than complex. This has profound implications on the role of the Bohmian classical-like interpretation of linear quantum mechanics, as well as on the possibilities to find a consistent interpretation of arbitrary nonlinear generalizations of quantum mechanics

  7. Quantum mechanics

    International Nuclear Information System (INIS)

    Anon.

    1990-01-01

    The book is on quantum mechanics. The emphasis is on the basic concepts and the methodology. The chapters include: Breakdown of classical concepts; Quantum mechanical concepts; Basic postulates of quantum mechanics; solution of problems in quantum mechanics; Simple harmonic oscillator; and Angular Momentum

  8. Mechanisms of mechanical strain memory in airway smooth muscle.

    Science.gov (United States)

    Kim, Hak Rim; Hai, Chi-Ming

    2005-10-01

    We evaluated the hypothesis that mechanical deformation of airway smooth muscle induces structural remodeling of airway smooth muscle cells, thereby modulating mechanical performance in subsequent contractions. This hypothesis implied that past experience of mechanical deformation was retained (or "memorized") as structural changes in airway smooth muscle cells, which modulated the cell's subsequent contractile responses. We termed this phenomenon mechanical strain memory. Preshortening has been found to induce attenuation of both force and isotonic shortening velocity in cholinergic receptor-activated airway smooth muscle. Rapid stretching of cholinergic receptor-activated airway smooth muscle from an initial length to a final length resulted in post-stretch force and myosin light chain phosphorylation that correlated significantly with initial length. Thus post-stretch muscle strips appeared to retain memory of the initial length prior to rapid stretch (mechanical strain memory). Cytoskeletal recruitment of actin- and integrin-binding proteins and Erk 1/2 MAPK appeared to be important mechanisms of mechanical strain memory. Sinusoidal length oscillation led to force attenuation during oscillation and in subsequent contractions in intact airway smooth muscle, and p38 MAPK appeared to be an important mechanism. In contrast, application of local mechanical strain to cultured airway smooth muscle cells induced local actin polymerization and cytoskeletal stiffening. It is conceivable that deep inspiration-induced bronchoprotection may be a manifestation of mechanical strain memory such that mechanical deformation from past breathing cycles modulated the mechanical performance of airway smooth muscle in subsequent cycles in a continuous and dynamic manner.

  9. 507 mechanical movements mechanisms and devices

    CERN Document Server

    Brown, Henry T

    2005-01-01

    Epicyclic trains, oblique rollers, trip hammers, and lazy-tongs are among the ingenious mechanisms defined and illustrated in this intriguing collection. Spanning the first century of the Industrial Revolution, this 1868 compilation features simplified, concise illustrations of the mechanisms used in hydraulics, steam engines, pneumatics, presses, horologes, and scores of other machines.The movements of each of the 507 mechanisms are depicted in drawings on the left-hand page, and the facing page presents a brief description of the item's use and operation. Ranging from simple to intricately c

  10. Radiation inactivation of T7 phage

    International Nuclear Information System (INIS)

    Becker, D.; Redpath, J.L.; Grossweiner, L.I.

    1978-01-01

    The radiation inactivation of T7 phage by 25-MeV electron pulses has been measured in various media containing a wide concentration range of radical scavenging solutes and in the presence of protective and sensitizing agents. The dependence of sensitivity on pulse dose, from 1 mrad to 3.6 krad, is attributed to radical depletion via bimolecular processes. The survival data are analyzed by extending target theory to include diffusive reactions of primary and secondary radicals generated in the medium. It is concluded that OH radicals are the principal primary inactivating species and that secondary radicals from Br - , CNS - , uracil, glucose, ribose, sucrose, tyrosine, and histidine are lethal to some extent. In nutrient broth or 100 mM histidine, psoralen derivatives, Actinomycin D, and Mitomycin C are anoxic sensitizers. It is proposed that the psoralens promote the formation of non-strand break lesions as the sensitization mechanism. The target theory based on diffusional kinetics is applicable to other systems including single cells

  11. Water oxidation catalyzed by mononuclear ruthenium complexes with a 2,2'-bipyridine-6,6'-dicarboxylate (bda) ligand: how ligand environment influences the catalytic behavior.

    Science.gov (United States)

    Staehle, Robert; Tong, Lianpeng; Wang, Lei; Duan, Lele; Fischer, Andreas; Ahlquist, Mårten S G; Sun, Licheng; Rau, Sven

    2014-02-03

    A new water oxidation catalyst [Ru(III)(bda)(mmi)(OH2)](CF3SO3) (2, H2bda = 2,2'-bipyridine-6,6'-dicarboxylic acid; mmi = 1,3-dimethylimidazolium-2-ylidene) containing an axial N-heterocyclic carbene ligand and one aqua ligand was synthesized and fully characterized. The kinetics of catalytic water oxidation by 2 were measured using stopped-flow technique, and key intermediates in the catalytic cycle were probed by density functional theory calculations. While analogous Ru-bda water oxidation catalysts [Ru(bda)L2] (L = pyridyl ligands) are supposed to catalyze water oxidation through a bimolecular coupling pathway, our study points out that 2, surprisingly, undergoes a single-site water nucleophilic attack (acid-base) pathway. The diversion of catalytic mechanisms is mainly ascribed to the different ligand environments, from nonaqua ligands to an aqua ligand. Findings in this work provide some critical proof for our previous hypothesis about how alternation of ancillary ligands of water oxidation catalysts influences their catalytic efficiency.

  12. Structure and Dynamics of Zr6O8 Metal-Organic Framework Node Surfaces Probed with Ethanol Dehydration as a Catalytic Test Reaction.

    Science.gov (United States)

    Yang, Dong; Ortuño, Manuel A; Bernales, Varinia; Cramer, Christopher J; Gagliardi, Laura; Gates, Bruce C

    2018-03-14

    Some metal-organic frameworks (MOFs) incorporate nodes that are metal oxide clusters such as Zr 6 O 8 . Vacancies on the node surfaces, accidental or by design, act as catalytic sites. Here, we report elucidation of the chemistry of Zr 6 O 8 nodes in the MOFs UiO-66 and UiO-67 having used infrared and nuclear magnetic resonance spectroscopies to determine the ligands on the node surfaces originating from the solvents and modifiers used in the syntheses and having elucidated the catalytic properties of the nodes for ethanol dehydration, which takes place selectively to make diethyl ether but not ethylene at 473-523 K. Density functional theory calculations show that the key to the selective catalysis is the breaking of node-linker bonds (or the accidental adjacency of open/defect sites) that allows catalytically fruitful bonding of the reactant ethanol to neighboring sites on the nodes, facilitating the bimolecular ether formation through an S N 2 mechanism.

  13. Barium: An Efficient Cathode Layer for Bulk-heterojunction Solar Cells

    Science.gov (United States)

    Gupta, Vinay; Kyaw, Aung Ko Ko; Wang, Dong Hwan; Chand, Suresh; Bazan, Guillermo C.; Heeger, Alan J.

    2013-01-01

    We report Barium (Ba) cathode layer for bulk-heterojunction solar cells which enhanced the fill factor (FF) of p-DTS(FBTTh2)2/PC71BM BHJ solar cell up to 75.1%, one of the highest value reported for an organic solar cell. The external quantum efficiency exceeds 80%. Analysis of recombination mechanisms using the current-voltage (J–V) characteristics at various light intensities in the BHJ solar cell layer reveals that Ba prevents trap assisted Shockley-Read-Hall (SRH) recombination at the interface and with different thicknesses of the Ba, the recombination shifts towards bimolecular from monomolecular. Moreover, Ba increases shunt resistance and decreases the series resistance significantly. This results in an increase in the charge collection probability leading to high FF. This work identifies a new cathode interlayer which outclasses the all the reported interlayers in increasing FF leading to high power conversion efficiency and have significant implications in improving the performance of BHJ solar cells. PMID:23752562

  14. Catalytic cracking of iso-hexene over sapo-34 catalyst

    International Nuclear Information System (INIS)

    Nawaz, Z.; Shu, Q.

    2009-01-01

    The catalytic cracking of model feed compound, iso-hexene (2-methyl-1-pentene) was experimentally studied over 100% pure SAPO-34 zeolite catalyst. The critical focus was given to obtain maximum propylene selectivity. The product distributions were analyzed at temperature between 450-600 degree C. time-on-stream (TOS) from 1 to 5 min. and at WHSV = 7.9 h/sub -1/ The reaction behavior was quantified on both direct and indirect carbenium ion mechanisms owing to catalyst's small pore diameter with respect to 2-methyl-l-pentene kinetic diameter. The propylene yield and selectivity obtained was 41.2% and 43.1% respectively. with higher overall olefins selectivity 90.3%. The small pore size and week surface acid sites of 1000 percent pure SAPO-34 catalyst were found to be suitable for light olefins production and eliminate chances of bimolecular reactions. It was observed that both conversion and selectivity were strongly effected by TOS, as coke precursors become dominant and deactivate catalyst at higher TOS. (author)

  15. Solvo-thermal in situ transesterification of wet spent coffee grounds for the production of biodiesel.

    Science.gov (United States)

    Park, Jeongseok; Kim, Bora; Son, Jeesung; Lee, Jae W

    2018-02-01

    This work addresses non-catalytic biodiesel production from spent coffee ground (SCG) by integrating solvo-thermal effect of 1,2-dichloroethane (DCE) with in situ transesterification over 160 °C. The SCG water content has a positive effect on the DCE hydrolysis up to 60 wt% due to the bimolecular substitution mechanism. The hydrolysis gives an acidic environment favorable for cellulose decomposition, SCG particle size reduction and lipid conversion. The optimal fatty acid ethyl ester yield was 11.8 wt% based on the mass of dried SCG with 3.36 ml ethanol and 3.16 ml DCE at 196.8 °C through the response surface methodology. Using the solvo-thermal effect, direct utilization of wet SCG as a biodiesel feedstock provides not only economic feasibility without using drying process and additional acid catalyst but also environmental advantage of recycling the municipal waste. Copyright © 2017 Elsevier Ltd. All rights reserved.

  16. Terahertz Conductivity within Colloidal CsPbBr3 Perovskite Nanocrystals: Remarkably High Carrier Mobilities and Large Diffusion Lengths.

    Science.gov (United States)

    Yettapu, Gurivi Reddy; Talukdar, Debnath; Sarkar, Sohini; Swarnkar, Abhishek; Nag, Angshuman; Ghosh, Prasenjit; Mandal, Pankaj

    2016-08-10

    Colloidal CsPbBr3 perovskite nanocrystals (NCs) have emerged as an excellent light emitting material in last one year. Using time domain and time-resolved THz spectroscopy and density functional theory based calculations, we establish 3-fold free carrier recombination mechanism, namely, nonradiative Auger, bimolecular electron-hole recombination, and inefficient trap-assisted recombination in 11 nm sized colloidal CsPbBr3 NCs. Our results confirm a negligible influence of surface defects in trapping charge carriers, which in turn results into desirable intrinsic transport properties, from the perspective of device applications, such as remarkably high carrier mobility (∼4500 cm(2) V(-1) s(-1)), large diffusion length (>9.2 μm), and high luminescence quantum yield (80%). Despite being solution processed and possessing a large surface to volume ratio, this combination of high carrier mobility and diffusion length, along with nearly ideal photoluminescence quantum yield, is unique compared to any other colloidal quantum dot system.

  17. Quantum Mechanics/Molecular Mechanics Modeling of Drug Metabolism

    DEFF Research Database (Denmark)

    Lonsdale, Richard; Fort, Rachel M; Rydberg, Patrik

    2016-01-01

    )-mexiletine in CYP1A2 with hybrid quantum mechanics/molecular mechanics (QM/MM) methods, providing a more detailed and realistic model. Multiple reaction barriers have been calculated at the QM(B3LYP-D)/MM(CHARMM27) level for the direct N-oxidation and H-abstraction/rebound mechanisms. Our calculated barriers......The mechanism of cytochrome P450(CYP)-catalyzed hydroxylation of primary amines is currently unclear and is relevant to drug metabolism; previous small model calculations have suggested two possible mechanisms: direct N-oxidation and H-abstraction/rebound. We have modeled the N-hydroxylation of (R...... indicate that the direct N-oxidation mechanism is preferred and proceeds via the doublet spin state of Compound I. Molecular dynamics simulations indicate that the presence of an ordered water molecule in the active site assists in the binding of mexiletine in the active site...

  18. Mechanics and Physics of Precise Vacuum Mechanisms

    CERN Document Server

    Deulin, E. A; Panfilov, Yu V; Nevshupa, R. A

    2010-01-01

    In this book the Russian expertise in the field of the design of precise vacuum mechanics is summarized. A wide range of physical applications of mechanism design in electronic, optical-electronic, chemical, and aerospace industries is presented in a comprehensible way. Topics treated include the method of microparticles flow regulation and its determination in vacuum equipment and mechanisms of electronics; precise mechanisms of nanoscale precision based on magnetic and electric rheology; precise harmonic rotary and not-coaxial nut-screw linear motion vacuum feedthroughs with technical parameters considered the best in the world; elastically deformed vacuum motion feedthroughs without friction couples usage; the computer system of vacuum mechanisms failure predicting. This English edition incorporates a number of features which should improve its usefulness as a textbook without changing the basic organization or the general philosophy of presentation of the subject matter of the original Russian work. Exper...

  19. Mechanics of Failure Mechanisms in Structures

    CERN Document Server

    Carlson, R L; Craig, J I

    2012-01-01

    This book focuses on the mechanisms and underlying mechanics of failure in various classes of materials such as metallic, ceramic, polymeric, composite and bio-material.  Topics include tensile and compressive fracture, crack initiation and growth, fatigue and creep rupture in metallic materials, matrix cracking and delamination and environmental degradation in polymeric composites, failure of bio-materials such as prosthetic heart valves and prosthetic hip joints, failure of ceramics and ceramic matrix composites, failure of metallic matrix composites, static and dynamic buckling failure, dynamic excitations and creep buckling failure in structural systems. Chapters are devoted to failure mechanisms that are characteristic of each of the materials.  The work also provides the basic elements of fracture mechanics and studies in detail several niche topics such as the effects of toughness gradients, variable amplitude loading effects in fatigue, small fatigue cracks, and creep induced brittleness. Furthe...

  20. Synthesis and antiacetylcholinesterase activity of new D-glyceraldehyde heterocyclic derivatives

    Energy Technology Data Exchange (ETDEWEB)

    Scorzo, Cecilia M.; Fascio, Mirta L.; D' Accorso, Norma B. [Universidad de Buenos Aires, Buenos Aires (Argentina). Facultad de Ciencias Exactas y Naturales. Dept. de Quimica Organica; Cabrera, Margarita Gutierrez; Saavedra, Luis Astudillo [Universidad de Talca (Chile). Inst. de Quimica de Productos Naturales. Lab. de Sintesis Organica

    2010-07-01

    We report herein the convenient procedures for the syntheses of different heterocyclic compounds from 2,3-O-isopropylidene-D-glyceraldehyde using intramolecular cyclization, 1,3-dipolar cycloaddition or bimolecular coupling reactions. The products were characterized by {sup 1}H and {sup 13}C NMR spectroscopy and elemental analysis. The new heterocycles and their derivatives were evaluated as inhibitors of acetylcholinesterase enzyme. (author)

  1. Synthesis and antiacetylcholinesterase activity of new D-glyceraldehyde heterocyclic derivatives

    International Nuclear Information System (INIS)

    Scorzo, Cecilia M.; Fascio, Mirta L.; D'Accorso, Norma B.; Cabrera, Margarita Gutierrez; Saavedra, Luis Astudillo

    2010-01-01

    We report herein the convenient procedures for the syntheses of different heterocyclic compounds from 2,3-O-isopropylidene-D-glyceraldehyde using intramolecular cyclization, 1,3-dipolar cycloaddition or bimolecular coupling reactions. The products were characterized by 1 H and 13 C NMR spectroscopy and elemental analysis. The new heterocycles and their derivatives were evaluated as inhibitors of acetylcholinesterase enzyme. (author)

  2. Discrete mechanics

    CERN Document Server

    Caltagirone, Jean-Paul

    2014-01-01

    This book presents the fundamental principles of mechanics to re-establish the equations of Discrete Mechanics. It introduces physics and thermodynamics associated to the physical modeling.  The development and the complementarity of sciences lead to review today the old concepts that were the basis for the development of continuum mechanics. The differential geometry is used to review the conservation laws of mechanics. For instance, this formalism requires a different location of vector and scalar quantities in space. The equations of Discrete Mechanics form a system of equations where the H

  3. Discrete mechanics

    International Nuclear Information System (INIS)

    Lee, T.D.

    1985-01-01

    This paper reviews the role of time throughout all phases of mechanics: classical mechanics, non-relativistic quantum mechanics, and relativistic quantum theory. As an example of the relativistic quantum field theory, the case of a massless scalar field interacting with an arbitrary external current is discussed. The comparison between the new discrete theory and the usual continuum formalism is presented. An example is given of a two-dimensional random lattice and its duel. The author notes that there is no evidence that the discrete mechanics is more appropriate than the usual continuum mechanics

  4. Mechanics of machinery

    CERN Document Server

    Mostafa, Mahmoud A

    2012-01-01

    MechanismsDefinitions Degrees of Freedom of Planar Mechanisms Four-Revolute-Pairs Chains Single-Slider Chain Double-Slider Mechanisms Mechanisms with Higher Pairs Compound Mechanisms Special Mechanisms Analytical Position Analysis of Mechanisms Velocities and AccelerationsAbsolute Plane Motion of a Particle Relative Motion Applications to Common Links Analysis of Mechanisms: Graphical Method Method of Instantaneous Centers for Determining the VelocitiesAnalytical Analysis CamsIntroduction Types of Cams Modes of Input/Output Motion Follower Configurations Classes of Cams Spur GearsIntroduction

  5. Teaching Continuum Mechanics in a Mechanical Engineering Program

    Science.gov (United States)

    Liu, Yucheng

    2011-01-01

    This paper introduces a graduate course, continuum mechanics, which is designed for and taught to graduate students in a Mechanical Engineering (ME) program. The significance of continuum mechanics in engineering education is demonstrated and the course structure is described. Methods used in teaching this course such as topics, class…

  6. Investigation into the Mechanism of Homo- and Heterodimerization of Angiotensin-Converting Enzyme.

    Science.gov (United States)

    Abrie, J Albert; Moolman, Wessel J A; Cozier, Gyles E; Schwager, Sylva L; Acharya, K Ravi; Sturrock, Edward D

    2018-04-01

    Angiotensin-converting enzyme (ACE) plays a central role in the renin-angiotensin system (RAS), which is primarily responsible for blood pressure homeostasis. Studies have shown that ACE inhibitors yield cardiovascular benefits that cannot be entirely attributed to the inhibition of ACE catalytic activity. It is possible that these benefits are due to interactions between ACE and RAS receptors that mediate the protective arm of the RAS, such as angiotensin II receptor type 2 (AT 2 R) and the receptor MAS. Therefore, in this study, we investigated the molecular interactions of ACE, including ACE homodimerization and heterodimerization with AT 2 R and MAS, respectively. Molecular interactions were assessed by fluorescence resonance energy transfer and bimolecular fluorescence complementation in human embryonic kidney 293 cells and Chinese hamster ovary-K1 cells transfected with vectors encoding fluorophore-tagged proteins. The specificity of dimerization was verified by competition experiments using untagged proteins. These techniques were used to study several potential requirements for the germinal isoform of angiotensin-converting enzyme expressed in the testes (tACE) dimerization as well as the effect of ACE inhibitors on both somatic isoforms of angiotensin-converting enzyme expressed in the testes (sACE) and tACE dimerization. We demonstrated constitutive homodimerization of sACE and of both of its domains separately, as well as heterodimerization of both sACE and tACE with AT 2 R, but not MAS. In addition, we investigated both soluble sACE and the sACE N domain using size-exclusion chromatography-coupled small-angle X-ray scattering and we observed dimers in solution for both forms of the enzyme. Our results suggest that ACE homo- and heterodimerization does occur under physiologic conditions. Copyright © 2018 by The American Society for Pharmacology and Experimental Therapeutics.

  7. Mechanical design

    CERN Document Server

    Risitano, Antonino

    2011-01-01

    METHODOLOGICAL STATEMENT OF ENGINEERING DESIGNApproaches to product design and developmentMechanical design and environmental requirementsPROPERTIES OF ENGINEERING MATERIALSMaterials for mechanical designCharacterization of metalsStress conditionsFatigue of materialsOptimum material selection in mechanical designDESIGN OF MECHANICAL COMPONENTS AND SYSTEMSFailure theoriesHertz theoryLubrificationShafts and bearingsSplines and keysSpringsFlexible machine elementsSpur gearsPress and shrink fitsPressure tubesCouplingsClutchesBrakes

  8. Material removal mechanisms in electrochemical-mechanical polishing of tantalum

    International Nuclear Information System (INIS)

    Gao, F.; Liang, H.

    2009-01-01

    Material removal mechanisms in tantalum chemical-mechanical polishing (CMP) and electrochemical-mechanical polishing (ECMP) were investigated using the single frequency electrochemical impedance spectroscopy (EIS). Through measuring the impedance of the tantalum surface, the single frequency EIS scan made it possible to observe the CMP and ECMP processes in situ. The impedance results presented competing mechanisms of removal and formation of a surface oxide layer of tantalum. Analysis indicated that the thickness of the oxide layer formed during polishing was related to the mechanical power correlated to the friction force and the rotating speed. Furthermore, the rate of growth and removal of the oxide film was a function of the mechanical power. This understanding is beneficial for optimization of CMP and ECMP processes.

  9. The Antikythera mechanism and the mechanical universe

    Science.gov (United States)

    Edmunds, M. G.

    2014-10-01

    How did our view of the Universe develop? By the mid-eighteenth century, a world view had developed of a system constrained by physical laws. These laws, if not entirely understood, showed regularity and could be handled mathematically to provide both explanation and prediction of celestial phenomena. Most of us have at least some hazy idea of the fundamental shift that came through the work of Copernicus, Kepler, Galileo and Newton. The idea of a 'Mechanical Universe' running rather like a clock tends to be associated with these sixteenth- and seventeenth-century pioneers. It remains a useful - and perhaps comforting - analogy. Yet, recent investigations based around the Antikythera Mechanism, an artefact from ancient Greece, reinforce a view that the 'Mechanical' conception has been around for a much longer time - indeed certainly as far back as the third century BC. The extent of mechanical design expertise existing around 100 BC as witnessed by the Antikythera Mechanism comes as a great surprise to most people. It is certainly a very ingenious device, often referred to as 'The World's First Computer' although it is really a sophisticated mechanical astronomical calculator with its functions pre-determined rather than programmable. In this review, the structure and functions of the Antikythera Mechanism are described. The astronomy, cosmology and technology inherent in the machine fit surprisingly well into the context of its contemporary Classical world. A strong claim will be made for the influence of such mechanisms on the development of astronomical and philosophical views, based on literary reference. There is evidence that the technology persisted until its spectacular and rather sudden re-appearance in Western Europe around 1300 AD. From then on it is not hard to chart a path through the astronomical clocks of the sixteenth century to Kepler's aim (expressed in a 1605 letter) to 'show that the heavenly machine is not a kind of divine, live being, but a

  10. Development of the ReaxFFCBN reactive force field for the improved design of liquid CBN hydrogen storage materials.

    Science.gov (United States)

    Pai, Sung Jin; Yeo, Byung Chul; Han, Sang Soo

    2016-01-21

    Liquid CBN (carbon-boron-nitrogen) hydrogen-storage materials such as 3-methyl-1,2-BN-cyclopentane have the advantage of being easily accessible for use in current liquid-fuel infrastructure. To develop practical liquid CBN hydrogen-storage materials, it is of great importance to understand the reaction pathways of hydrogenation/dehydrogenation in the liquid phase, which are difficult to discover by experimental methods. Herein, we developed a reactive force field (ReaxFFCBN) from quantum mechanical (QM) calculations based on density functional theory for the storage of hydrogen in BN-substituted cyclic hydrocarbon materials. The developed ReaxFFCBN provides similar dehydrogenation pathways and energetics to those predicted by QM calculations. Moreover, molecular dynamics (MD) simulations with the developed ReaxFFCBN can predict the stability and dehydrogenation behavior of various liquid CBN hydrogen-storage materials. Our simulations reveal that a unimolecular dehydrogenation mechanism is preferred in liquid CBN hydrogen-storage materials. However, as the temperature in the simulation increases, the contribution of a bimolecular dehydrogenation mechanism also increases. Moreover, our ReaxFF MD simulations show that in terms of thermal stability and dehydrogenation kinetics, liquid CBN materials with a hexagonal structure are more suitable materials than those with a pentagonal structure. We expect that the developed ReaxFFCBN could be a useful protocol in developing novel liquid CBN hydrogen-storage materials.

  11. Mechanical engineers' handbook, materials and engineering mechanics

    CERN Document Server

    Kutz, Myer

    2015-01-01

    Full coverage of materials and mechanical design inengineering Mechanical Engineers' Handbook, Fourth Edition provides aquick guide to specialized areas you may encounter in your work,giving you access to the basics of each and pointing you towardtrusted resources for further reading, if needed. The accessibleinformation inside offers discussions, examples, and analyses ofthe topics covered. This first volume covers materials and mechanical design, givingyou accessible and in-depth access to the most common topics you'llencounter in the discipline: carbon and alloy steels, stainlesssteels, a

  12. NLC Mechanical

    Science.gov (United States)

    text only Mechanical Systems.gif (14697 bytes) NLC Home Page NLC Technical SLAC Permanent Magnets Organization Overview The Mechanical Systems Group Organization is shown on the NLC Project Group Organization Chart (Next Linear Collider Technical Web Page). The Mechanical Systems Group operates on a matrixed

  13. Tokamak engineering mechanics

    International Nuclear Information System (INIS)

    Song, Yuntao; Wu, Weiyue; Du, Shijun

    2014-01-01

    Provides a systematic introduction to tokamaks in engineering mechanics. Includes design guides based on full mechanical analysis, which makes it possible to accurately predict load capacity and temperature increases. Presents comprehensive information on important design factors involving materials. Covers the latest advances in and up-to-date references on tokamak devices. Numerous examples reinforce the understanding of concepts and provide procedures for design. Tokamak Engineering Mechanics offers concise and thorough coverage of engineering mechanics theory and application for tokamaks, and the material is reinforced by numerous examples. Chapter topics include general principles, static mechanics, dynamic mechanics, thermal fluid mechanics and multiphysics structural mechanics of tokamak structure analysis. The theoretical principle of the design and the methods of the analysis for various components and load conditions are presented, while the latest engineering technologies are also introduced. The book will provide readers involved in the study of mechanical/fusion engineering with a general understanding of tokamak engineering mechanics.

  14. Mechanical engineering education

    CERN Document Server

    Davim, J Paulo

    2012-01-01

    Mechanical Engineering is defined nowadays as a discipline "which involves the application of principles of physics, design, manufacturing and maintenance of mechanical systems". Recently, mechanical engineering has also focused on some cutting-edge subjects such as nanomechanics and nanotechnology, mechatronics and robotics, computational mechanics, biomechanics, alternative energies, as well as aspects related to sustainable mechanical engineering.This book covers mechanical engineering higher education with a particular emphasis on quality assurance and the improvement of academic

  15. Investigation of the structure and properties of heterocyclic compounds and their complexes

    International Nuclear Information System (INIS)

    Shejnker, V.N.; Troilina, V.S.; Merinova, E.G.; Garnovskij, A.D.; Osipov, O.A.

    1988-01-01

    Complexing of acetyl derivatives of azoles with iodine and bromine iodide is investigated using UV-spectroscopy and dipole moment methods. In bimolecular complexes σ-acceptor coordination occurs by heterocycle pyridine type nitrogen atom and is not accompanied by the ligand conformation change. The complex stability increases in agreement with azole basicity. For N-acetyltriazole ligand, conformation reversal occurs in its trimolecular complex with IBr

  16. Photochemical reaction dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Moore, B.C. [Lawrence Berkeley Laboratory, Livermore, CA (United States)

    1993-12-01

    The purpose of the program is to develop a fundamental understanding of unimolecular and bimolecular reaction dynamics with application in combustion and energy systems. The energy dependence in ketene isomerization, ketene dissociation dynamics, and carbonyl substitution on organometallic rhodium complexes in liquid xenon have been studied. Future studies concerning unimolecular processes in ketene as well as energy transfer and kinetic studies of methylene radicals are discussed.

  17. Method and apparatus for isotope separation from a gas stream

    International Nuclear Information System (INIS)

    Szoke, A.

    1978-01-01

    A method and apparatus are described for isotope separation and in particular for separating the desired isotope from the gas in which it is contained by irradiating it with a laser. The laser selectively provides kinetic energy to the isotope through inelastic events, monomolecular or bimolecular, in order to cause it to segregate within or fly out of the gas stream in which it is contained

  18. Can macular xanthophylls replace cholesterol in formation of the liquid-ordered phase in lipid-bilayer membranes?

    OpenAIRE

    Subczynski, Witold K.; Wisniewska, Anna; Widomska, Justyna

    2012-01-01

    Lateral organization of membranes made from binary mixtures of dimyristoylphosphatidylcholine (DMPC) or dipalmitoylphosphatidylcholine (DPPC) and macular xanthophylls (lutein or zeaxanthin) was investigated using the saturation-recovery (SR) EPR spin-labeling discrimination by oxygen transport (DOT) method in which the bimolecular collision rate of molecular oxygen with the nitroxide spin label is measured. This work was undertaken to examine whether or not lutein and zeaxanthin, macular xant...

  19. Analogies between classical statistical mechanics and quantum mechanics

    International Nuclear Information System (INIS)

    Uehara, M.

    1986-01-01

    Some analogies between nonequilibrium classical statistical mechanics and quantum mechanics, at the level of the Liouville equation and at the kinetic level, are commented on. A theorem, related to the Vlasov equation applied to a plasma, is proved. The theorem presents an analogy with Ehrenfest's theorem of quantum mechanics. An analogy between the plasma kinetic theory and Bohm's quantum theory with 'hidden variables' is also shown. (Author) [pt

  20. Continuum Mechanics

    CERN Document Server

    Romano, Antonio

    2010-01-01

    This book offers a broad overview of the potential of continuum mechanics to describe a wide range of macroscopic phenomena in real-world problems. Building on the fundamentals presented in the authors' previous book, Continuum Mechanics using Mathematica(R), this new work explores interesting models of continuum mechanics, with an emphasis on exploring the flexibility of their applications in a wide variety of fields.Specific topics, which have been chosen to show the power of continuum mechanics to characterize the experimental behavior of real phenomena, include: * various aspects of nonlin

  1. Mechanical engineer's handbook

    CERN Document Server

    Marghitu, Dan B

    2001-01-01

    The Mechanical Engineer's Handbook was developed and written specifically to fill a need for mechanical engineers and mechanical engineering students throughout the world. With over 1000 pages, 550 illustrations, and 26 tables the Mechanical Engineer's Handbook is very comprehensive, yet affordable, compact, and durable. The Handbook covers all major areas of mechanical engineering with succinct coverage of the definitions, formulas, examples, theory, proofs, and explanations of all principle subject areas. The Handbook is an essential, practical companion for all mechanic

  2. Tokamak engineering mechanics

    CERN Document Server

    Song, Yuntao; Du, Shijun

    2013-01-01

    Tokamak Engineering Mechanics offers concise and thorough coverage of engineering mechanics theory and application for tokamaks, and the material is reinforced by numerous examples. Chapter topics include general principles, static mechanics, dynamic mechanics, thermal fluid mechanics and multiphysics structural mechanics of tokamak structure analysis. The theoretical principle of the design and the methods of the analysis for various components and load conditions are presented, while the latest engineering technologies are also introduced. The book will provide readers involved in the study

  3. Foundations of mechanics

    International Nuclear Information System (INIS)

    Zorski, Henryk; Bazanski, Stanislaw; Gutowski, Roman; Slawianowski, Jan; Wilmanski, Krysztof; Wozniak, Czeslaw

    1992-01-01

    In the last 3 decades the field of mechanics has seen spectacular progress due to the demand for applications in problems of cosmology, thermonuclear fusion, metallurgy, etc. This book provides a broad and thorough overview on the foundations of mechanics. It discusses theoretical mechanics and continuum mechanics, as well as phenomenological thermodynamics, quantum mechanics and relativistic mechanics. Each chapter presents the basic physical facts of interest without going into details and derivations and without using advanced mathematical formalism. The first part constitutes a classical exposition of Lagrange's and Hamiltonian's analytical mechanics on which most of the continuum theory is based. The section on continuum mechanics focuses mainly on the axiomatic foundations, with many pointers for further research in this area. Special attention is given to modern continuum thermodynamics, both for the foundations and applications. A section on quantum mechanics is also included, since the phenomenological description of various quantum phenomena is becoming of increasing importance. refs.; figs.; tabs

  4. Martensite and bainite in steels: transformation mechanism and mechanical properties

    International Nuclear Information System (INIS)

    Bhadeshia, H.K.D.H.

    1997-01-01

    Many essential properties of iron alloys depend on what actually happens when one allotropic form gives way to another, i.e. on the mechanism of phase change. The dependence of the mechanical properties on the atomic mechanism by which bainite and martensite grow is the focus of this paper. The discussion is illustrated in the context of some common engineering design parameters, and with a brief example of the inverse problem in which the mechanism may be a function of the mechanical properties. (orig.)

  5. Leaching mechanisms

    International Nuclear Information System (INIS)

    Dougherty, D.R.; Colombo, P.

    1984-01-01

    Sufficient data are lacking to provide a basis for adequately assessing the long term leaching behavior of solidified low level radioactive waste forms in their disposal environment. Although the release of radioactivity from a waste form to an aqueous environment is recognized to be due to one or more mechanisms such as diffusion, dissolution, corrosion or ion exchange, the leaching mechanisms and the factors which control the leaching behavior of waste forms are not fully understood. This study will determine the prevailing mechanisms for a variety of selected LLW solidification agents which are being considered for use by defense and commercial generators and which will cover the broadest possible number of mechanisms. The investigation will proceed by the postulation of mathematical models representative of the prevailing mechanism(s) and the use of statistically designed experiments to test the actual leaching behavior of laborattory samples against the postulated representations. Maximum use of existing leach data in the literature will be made by incorporating literature results into a computerized data base along with the experimental results generated in this task

  6. Mechanical Kinesiology.

    Science.gov (United States)

    Barham, Jerry N.

    Mechanical kinesiology is defined as a study of the mechanical factors affecting human movement, i.e., applying the physical laws of mechanics to the study of human motor behavior. This textbook on the subject is divided into thirty lessons. Each lesson is organized into three parts: a part on the text proper; a part entitled "study…

  7. Genomic interrogation of mechanism(s) underlying cellular responses to toxicants

    International Nuclear Information System (INIS)

    Amin, Rupesh P.; Hamadeh, Hisham K.; Bushel, Pierre R.; Bennett, Lee; Afshari, Cynthia A.; Paules, Richard S.

    2002-01-01

    Assessment of the impact of xenobiotic exposure on human health and disease progression is complex. Knowledge of mode(s) of action, including mechanism(s) contributing to toxicity and disease progression, is valuable for evaluating compounds. Toxicogenomics, the subdiscipline which merges genomics with toxicology, holds the promise to contributing significantly toward the goal of elucidating mechanism(s) by studying genome-wide effects of xenobiotics. Global gene expression profiling, revolutionized by microarray technology and a crucial aspect of a toxicogenomic study, allows measuring transcriptional modulation of thousands of genes following exposure to a xenobiotic. We use our results from previous studies on compounds representing two different classes of xenobiotics (barbiturate and peroxisome proliferator) to discuss the application of computational approaches for analyzing microarray data to elucidate mechanism(s) underlying cellular responses to toxicants. In particular, our laboratory demonstrated that chemical-specific patterns of gene expression can be revealed using cDNA microarrays. Transcript profiling provides discrimination between classes of toxicants, as well as, genome-wide insight into mechanism(s) of toxicity and disease progression. Ultimately, the expectation is that novel approaches for predicting xenobiotic toxicity in humans will emerge from such information

  8. Impact of OH Radical-Initiated H2CO3 Degradation in the Earth's Atmosphere via Proton-Coupled Electron Transfer Mechanism.

    Science.gov (United States)

    Ghoshal, Sourav; Hazra, Montu K

    2016-02-04

    The decomposition of isolated carbonic acid (H2CO3) molecule into CO2 and H2O (H2CO3 → CO2 + H2O) is prevented by a large activation barrier (>35 kcal/mol). Nevertheless, it is surprising that the detection of the H2CO3 molecule has not been possible yet, and the hunt for the free H2CO3 molecule has become challenging not only in the Earth's atmosphere but also on Mars. In view of this fact, we report here the high levels of quantum chemistry calculations investigating both the energetics and kinetics of the OH radical-initiated H2CO3 degradation reaction to interpret the loss of the H2CO3 molecule in the Earth's atmosphere. It is seen from our study that proton-coupled electron transfer (PCET) and hydrogen atom transfer (HAT) are the two mechanisms by which the OH radical initiates the degradation of the H2CO3 molecule. Moreover, the PCET mechanism is potentially the important one, as the effective barrier, defined as the difference between the zero point vibrational energy (ZPE) corrected energy of the transition state and the total energy of the isolated starting reactants in terms of bimolecular encounters, for the PCET mechanism at the CCSD(T)/6-311++G(3df,3pd) level of theory is ∼3 to 4 kcal/mol lower than the effective barrier height associated with the HAT mechanism. The CCSD(T)/6-311++G(3df,3pd) level predicted effective barrier heights for the degradations of the two most stable conformers of H2CO3 molecule via the PCET mechanism are only ∼2.7 and 4.3 kcal/mol. A comparative reaction rate analysis at the CCSD(T)/6-311++G(3df,3pd) level of theory has also been carried out to explore the potential impact of the OH radical-initiated H2CO3 degradation relative to that from water (H2O), formic acid (FA), acetic acid (AA) and sulfuric acid (SA) assisted H2CO3 → CO2 + H2O decomposition reactions in both the Earth's troposphere and stratosphere. The comparison of the reaction rates reveals that, although the atmospheric concentration of the OH radical is

  9. College mechanics

    CERN Document Server

    Şengül, Caner

    2016-01-01

    College Mechanics QueBank has been designed to be different, enthusiastic, interesting and helpful to you. Therefore, it is not just a test bank about mechanics but also it is like a compass in order to find your way in mechanics Each chapter in this book is put in an order to follow a hierarchy of the mechanics topics; from vectors to simple harmonic motion. Throughout the book there are many multiple choice and long answer questions for you to solve. They have been created for YGS, LYS, SAT, IB or other standardized exams in the world because mechanics has no boundaries and so Physics has no country. Learn the main principle of each chapter and explore the daily life applications. Then you can start to solve the questions by planning a problem solving method carefully. Finally, enjoy solving the questions and discover the meachanics of the universe once more.

  10. Electron transfer function versus oxygen delivery: a comparative study for several hexacoordinated globins across the animal kingdom.

    Science.gov (United States)

    Kiger, Laurent; Tilleman, Lesley; Geuens, Eva; Hoogewijs, David; Lechauve, Christophe; Moens, Luc; Dewilde, Sylvia; Marden, Michael C

    2011-01-01

    Caenorhabditis elegans globin GLB-26 (expressed from gene T22C1.2) has been studied in comparison with human neuroglobin (Ngb) and cytoglobin (Cygb) for its electron transfer properties. GLB-26 exhibits no reversible binding for O(2) and a relatively low CO affinity compared to myoglobin-like globins. These differences arise from its mechanism of gaseous ligand binding since the heme iron of GLB-26 is strongly hexacoordinated in the absence of external ligands; the replacement of this internal ligand, probably the E7 distal histidine, is required before binding of CO or O(2) as for Ngb and Cygb. Interestingly the ferrous bis-histidyl GLB-26 and Ngb, another strongly hexacoordinated globin, can transfer an electron to cytochrome c (Cyt-c) at a high bimolecular rate, comparable to those of inter-protein electron transfer in mitochondria. In addition, GLB-26 displays an unexpectedly rapid oxidation of the ferrous His-Fe-His complex without O(2) actually binding to the iron atom, since the heme is oxidized by O(2) faster than the time for distal histidine dissociation. These efficient mechanisms for electron transfer could indicate a family of hexacoordinated globin which are functionally different from that of pentacoordinated globins.

  11. Mechanistic Study of the Gas-Phase In-Source Hofmann Elimination of Doubly Quaternized Cinchona-Alkaloid Based Phase-Transfer Catalysts by (+)-Electrospray Ionization/Tandem Mass Spectrometry

    Science.gov (United States)

    Yang, Rong-Sheng; Sheng, Huaming; Lexa, Katrina W.; Sherer, Edward C.; Zhang, Li-Kang; Xiang, Bangping; Helmy, Roy; Mao, Bing

    2017-03-01

    An unusual in-source fragmentation pattern observed for 14 doubly quaternized cinchona alkaloid-based phase-transfer catalysts (PTC) was studied using (+)-ESI high resolution mass spectrometry. Loss of the substituted benzyl cation (R1 or R2) was found to be the major product ion [M2+ - R1 + or R2 +]+ in MS spectra of all PTC compounds. A Hofmann elimination product ion [M - H]+ was also observed. Only a small amount of the doubly charged M2+ ions were observed in the MS spectra, likely due to strong Columbic repulsion between the two quaternary ammonium cations in the gas phase. The positive voltage in the MS inlet but not the ESI probe was found to induce this extensive fragmentation for all PTC diboromo-salts. Compound 1 was used as an example to illustrate the proposed in-source fragmentation mechanism. The mechanism of formation of the Hofmann elimination product ion [M - H]+ was further investigated using HRMS/MS, H/D exchange, and DFT calculations. The proposed formation of 2b as the major Hofmann elimination product ion was supported both by HRMS/MS and DFT calculations. Formation of product ion 2b through a concerted unimolecular Ei elimination pathway is proposed rather than a bimolecular E2 elimination pathway for common solution Hofmann eliminations.

  12. A combined crossed molecular beam and theoretical investigation of the reaction of the meta-tolyl radical with vinylacetylene--toward the formation of methylnaphthalenes.

    Science.gov (United States)

    Yang, Tao; Muzangwa, Lloyd; Kaiser, Ralf I; Jamal, Adeel; Morokuma, Keiji

    2015-09-07

    Crossed molecular beam experiments and electronic structure calculations on the reaction of the meta-tolyl radical with vinylacetylene were conducted to probe the formation of methyl-substituted naphthalene isomers. We present the compelling evidence that under single collision conditions 1- and 2-methylnaphthalene can be formed without an entrance barrier via indirect scattering dynamics through a bimolecular collision of two non-PAH reactants: the meta-tolyl radical and vinylacetylene. The electronic structure calculations, conducted at the UCCSD(T)-F12b/cc-pVDZ//UM06-2x/cc-pVTZ + ZPE(UM06-2x/cc-pVTZ) level of theory, reveal that this reaction is initiated by the barrierless addition of the meta-tolyl radical to the terminal vinyl carbon (C1) of vinylacetylene, via a van-der-Waals complex implying that this mechanism can play a key role in forming methyl-substituted PAHs in low temperature extreme environments such as the low temperature interstellar medium and hydrocarbon-rich atmospheres of planets and their moons in the outer solar system. The reaction mechanism, proposed from the C11H11 potential energy surface, involves a sequence of isomerizations involving hydrogen transfer and ring closure, followed by hydrogen dissociation, which eventually leads to 1- and 2-methylnaphthalene in an overall exoergic process.

  13. Understanding the mechanisms of lung mechanical stress

    Directory of Open Access Journals (Sweden)

    C.S.N.B. Garcia

    2006-06-01

    Full Text Available Physical forces affect both the function and phenotype of cells in the lung. Bronchial, alveolar, and other parenchymal cells, as well as fibroblasts and macrophages, are normally subjected to a variety of passive and active mechanical forces associated with lung inflation and vascular perfusion as a result of the dynamic nature of lung function. These forces include changes in stress (force per unit area or strain (any forced change in length in relation to the initial length and shear stress (the stress component parallel to a given surface. The responses of cells to mechanical forces are the result of the cell's ability to sense and transduce these stimuli into intracellular signaling pathways able to communicate the information to its interior. This review will focus on the modulation of intracellular pathways by lung mechanical forces and the intercellular signaling. A better understanding of the mechanisms by which lung cells transduce physical forces into biochemical and biological signals is of key importance for identifying targets for the treatment and prevention of physical force-related disorders.

  14. Respiratory mechanics

    CERN Document Server

    Wilson, Theodore A

    2016-01-01

    This book thoroughly covers each subfield of respiratory mechanics: pulmonary mechanics, the respiratory pump, and flow. It presents the current understanding of the field and serves as a guide to the scientific literature from the golden age of respiratory mechanics, 1960 - 2010. Specific topics covered include the contributions of surface tension and tissue forces to lung recoil, the gravitational deformation of the lung, and the interdependence forces that act on pulmonary airways and blood vessels. The geometry and kinematics of the ribs is also covered in detail, as well as the respiratory action of the external and internal intercostal muscles, the mechanics of the diaphragm, and the quantitative compartmental models of the chest wall is also described. Additionally, flow in the airways is covered thoroughly, including the wave-speed and viscous expiratory flow-limiting mechanisms; convection, diffusion and the stationary front; and the distribution of ventilation. This is an ideal book for respiratory ...

  15. Quantum mechanics

    CERN Document Server

    Rae, Alastair I M

    2016-01-01

    A Thorough Update of One of the Most Highly Regarded Textbooks on Quantum Mechanics Continuing to offer an exceptionally clear, up-to-date treatment of the subject, Quantum Mechanics, Sixth Edition explains the concepts of quantum mechanics for undergraduate students in physics and related disciplines and provides the foundation necessary for other specialized courses. This sixth edition builds on its highly praised predecessors to make the text even more accessible to a wider audience. It is now divided into five parts that separately cover broad topics suitable for any general course on quantum mechanics. New to the Sixth Edition * Three chapters that review prerequisite physics and mathematics, laying out the notation, formalism, and physical basis necessary for the rest of the book * Short descriptions of numerous applications relevant to the physics discussed, giving students a brief look at what quantum mechanics has made possible industrially and scientifically * Additional end-of-chapter problems with...

  16. Fracture Mechanics

    CERN Document Server

    Zehnder, Alan T

    2012-01-01

    Fracture mechanics is a vast and growing field. This book develops the basic elements needed for both fracture research and engineering practice. The emphasis is on continuum mechanics models for energy flows and crack-tip stress- and deformation fields in elastic and elastic-plastic materials. In addition to a brief discussion of computational fracture methods, the text includes practical sections on fracture criteria, fracture toughness testing, and methods for measuring stress intensity factors and energy release rates. Class-tested at Cornell, this book is designed for students, researchers and practitioners interested in understanding and contributing to a diverse and vital field of knowledge. Alan Zehnder joined the faculty at Cornell University in 1988. Since then he has served in a number of leadership roles including Chair of the Department of Theoretical and Applied Mechanics, and Director of the Sibley School of Mechanical and Aerospace Engineering.  He teaches applied mechanics and his research t...

  17. Mechanical seal assembly

    Science.gov (United States)

    Kotlyar, Oleg M.

    2001-01-01

    An improved mechanical seal assembly is provided for sealing rotating shafts with respect to their shaft housings, wherein the rotating shafts are subject to substantial axial vibrations. The mechanical seal assembly generally includes a rotating sealing ring fixed to the shaft, a non-rotating sealing ring adjacent to and in close contact with the rotating sealing ring for forming an annular seal about the shaft, and a mechanical diode element that applies a biasing force to the non-rotating sealing ring by means of hemispherical joint. The alignment of the mechanical diode with respect to the sealing rings is maintained by a series of linear bearings positioned axially along a desired length of the mechanical diode. Alternative embodiments include mechanical or hydraulic amplification components for amplifying axial displacement of the non-rotating sealing ring and transferring it to the mechanical diode.

  18. Mechanical Seal Assembly

    Energy Technology Data Exchange (ETDEWEB)

    Kotlyar, Oleg M.

    1999-06-18

    An improved mechanical seal assembly is provided for sealing rotating shafts with respect to their shaft housings, wherein the rotating shafts are subject to substantial axial vibrations. The mechanical seal assembly generally includes a rotating sealing ring fixed to the shaft, a non-rotating sealing ring adjacent to and in close contact with the rotating sealing ring for forming an annular seal about the shaft, and a mechanical diode element that applies a biasing force to the non-rotating sealing ring by means of hemispherical joint. The alignment of the mechanical diode with respect to the sealing rings is maintained by a series of linear bearings positioned axially along a desired length of the mechanical diode. Alternative embodiments include mechanical or hydraulic amplification components for amplifying axial displacement of the non-rotating sealing ring and transferring it to the mechanical diode.

  19. Mechanical drawing

    Energy Technology Data Exchange (ETDEWEB)

    Cho, Ho Seon; Lee, Geun Hui

    2004-04-15

    This book deals with how to read and draw the mechanical drawing, which includes the basic of drawing like purpose, kinds, and criterion, projection, special projection drawing, omission of the figure, section, and types of section, dimensioning method, writing way of allowable limit size, tolerance of regular size, parts list and assembling drawing, fitting, mechanical elements like screw, key, pin, rivet, spring, bearing, pipe, valve, welding, geometric tolerance and mechanical materials.

  20. Classical mechanics

    CERN Document Server

    Benacquista, Matthew J

    2018-01-01

    This textbook provides an introduction to classical mechanics at a level intermediate between the typical undergraduate and advanced graduate level. This text describes the background and tools for use in the fields of modern physics, such as quantum mechanics, astrophysics, particle physics, and relativity. Students who have had basic undergraduate classical mechanics or who have a good understanding of the mathematical methods of physics will benefit from this book.

  1. Supersymmetric mechanics

    International Nuclear Information System (INIS)

    Stelle, Kellogg S

    2007-01-01

    With the development of the electronic archives in high-energy physics, there has been increasing questioning of the role of traditional publishing styles, particularly in the production of conference books. One aspect of traditional publishing that still receives wide appreciation, however, is in the production of well-focussed pedagogical material. The present two-volume edition, 'Supersymmetric Mechanics-Vol 1', edited by S Bellucci and 'Supersymmetric Mechanics-Vol 2', edited by S Bellucci, S Ferrara and A Marrani, is a good example of the kind of well-digested presentation that should still find its way into university libraries. This two-volume set presents the material of a set of pedagogical lectures presented at the INFN National Laboratory in Frascati over a two-year period on the subject of supersymmetric mechanics. The articles include the results of discussions with the attending students after the lectures. Overall, this makes for a useful compilation of material on a subject that underlies much of the current effort in supersymmetric approaches to cosmology and the unification programme. The first volume comprises articles on 'A journey through garden algebras' by S Bellucci, S J Gates Jr and E Orazi on linear supermultiplet realizations in supersymmetric mechanics,'Supersymmetric mechanics in superspace' by S Bellucci and S Krivonos, 'Noncommutative mechanics, Landau levels, twistors and Yang-Mills amplitudes' by V P Nair, 'Elements of (super) Hamiltonian formalism' by A Nersessian and 'Matrix mechanics' by C Sochichiu. The second volume consists entirely of a masterful presentation on 'The attractor mechanism and space time singularities' by S Ferrara. This presents a comprehensive and detailed overview of the structure of supersymmetric black hole solutions in supergravity, critical point structure in the scalar field moduli space and the thermodynamic consequences. This second volume alone makes the set a worthwhile addition to the research

  2. Uncovering the mechanism(s) of deep brain stimulation

    International Nuclear Information System (INIS)

    Li Gang; Yu Chao; Lin Ling; Lu, Stephen C-Y

    2005-01-01

    Deep brain stimulators, often called 'pacemakers for the brain', are implantable devices which continuously deliver impulse stimulation to specific targeted nuclei of deep brain structure, namely deep brain stimulation (DBS). To date, deep brain stimulation (DBS) is the most effective clinical technique for the treatment of several medically refractory movement disorders (e.g., Parkinson's disease, essential tremor, and dystonia). In addition, new clinical applications of DBS for other neurologic and psychiatric disorders (e.g., epilepsy and obsessive-compulsive disorder) have been put forward. Although DBS has been effective in the treatment of movement disorders and is rapidly being explored for the treatment of other neurologic disorders, the scientific understanding of its mechanisms of action remains unclear and continues to be debated in the scientific community. Optimization of DBS technology for present and future therapeutic applications will depend on identification of the therapeutic mechanism(s) of action. The goal of this review is to address our present knowledge of the effects of high-frequency stimulation within the central nervous system and comment on the functional implications of this knowledge for uncovering the mechanism(s) of DBS

  3. Extended quantum mechanics

    International Nuclear Information System (INIS)

    Pavel Bona

    2000-01-01

    The work can be considered as an essay on mathematical and conceptual structure of nonrelativistic quantum mechanics which is related here to some other (more general, but also to more special and 'approximative') theories. Quantum mechanics is here primarily reformulated in an equivalent form of a Poisson system on the phase space consisting of density matrices, where the 'observables', as well as 'symmetry generators' are represented by a specific type of real valued (densely defined) functions, namely the usual quantum expectations of corresponding selfjoint operators. It is shown in this paper that inclusion of additional ('nonlinear') symmetry generators (i. e. 'Hamiltonians') into this reformulation of (linear) quantum mechanics leads to a considerable extension of the theory: two kinds of quantum 'mixed states' should be distinguished, and operator - valued functions of density matrices should be used in the role of 'nonlinear observables'. A general framework for physical theories is obtained in this way: By different choices of the sets of 'nonlinear observables' we obtain, as special cases, e.g. classical mechanics on homogeneous spaces of kinematical symmetry groups, standard (linear) quantum mechanics, or nonlinear extensions of quantum mechanics; also various 'quasiclassical approximations' to quantum mechanics are all sub theories of the presented extension of quantum mechanics - a version of the extended quantum mechanics. A general interpretation scheme of extended quantum mechanics extending the usual statistical interpretation of quantum mechanics is also proposed. Eventually, extended quantum mechanics is shown to be (included into) a C * -algebraic (hence linear) quantum theory. Mathematical formulation of these theories is presented. The presentation includes an analysis of problems connected with differentiation on infinite-dimensional manifolds, as well as a solution of some problems connected with the work with only densely defined unbounded

  4. CHEMICAL REACTIONS ON ADSORBING SURFACE: KINETIC LEVEL OF DESCRIPTION

    Directory of Open Access Journals (Sweden)

    P.P.Kostrobii

    2003-01-01

    Full Text Available Based on the effective Hubbard model we suggest a statistical description of reaction-diffusion processes for bimolecular chemical reactions of gas particles adsorbed on the metallic surface. The system of transport equations for description of particles diffusion as well as reactions is obtained. We carry out the analysis of the contributions of all physical processes to the formation of diffusion coefficients and chemical reactions constants.

  5. Sectoral Market Mechanisms

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    2009-07-01

    This paper first reviews proposals for the design of sectoral and related market mechanisms currently debated, both in the UNFCCC negotiations, and in different domestic legislative contexts. Secondly, it addresses the possible principles and technical requirements that Parties may wish to consider as the foundations for further elaboration of the mechanisms. The third issue explored herein is domestic implementation of sectoral market mechanisms by host countries, incentives to move to new market mechanisms, as well as how the transition between current and future mechanisms could be managed.

  6. Quantum mechanics and stochastic mechanics for compatible observables at different times

    International Nuclear Information System (INIS)

    Correggi, M.; Morchio, G.

    2002-01-01

    Bohm mechanics and Nelson stochastic mechanics are confronted with quantum mechanics in the presence of noninteracting subsystems. In both cases, it is shown that correlations at different times of compatible position observables on stationary states agree with quantum mechanics only in the case of product wave functions. By appropriate Bell-like inequalities it is shown that no classical theory, in particular no stochastic process, can reproduce the quantum mechanical correlations of position variables of noninteracting systems at different times

  7. Bacterial Cell Mechanics.

    Science.gov (United States)

    Auer, George K; Weibel, Douglas B

    2017-07-25

    Cellular mechanical properties play an integral role in bacterial survival and adaptation. Historically, the bacterial cell wall and, in particular, the layer of polymeric material called the peptidoglycan were the elements to which cell mechanics could be primarily attributed. Disrupting the biochemical machinery that assembles the peptidoglycan (e.g., using the β-lactam family of antibiotics) alters the structure of this material, leads to mechanical defects, and results in cell lysis. Decades after the discovery of peptidoglycan-synthesizing enzymes, the mechanisms that underlie their positioning and regulation are still not entirely understood. In addition, recent evidence suggests a diverse group of other biochemical elements influence bacterial cell mechanics, may be regulated by new cellular mechanisms, and may be triggered in different environmental contexts to enable cell adaptation and survival. This review summarizes the contributions that different biomolecular components of the cell wall (e.g., lipopolysaccharides, wall and lipoteichoic acids, lipid bilayers, peptidoglycan, and proteins) make to Gram-negative and Gram-positive bacterial cell mechanics. We discuss the contribution of individual proteins and macromolecular complexes in cell mechanics and the tools that make it possible to quantitatively decipher the biochemical machinery that contributes to bacterial cell mechanics. Advances in this area may provide insight into new biology and influence the development of antibacterial chemotherapies.

  8. Mechanism of deactivation of triplet-excited riboflavin by ascorbate, carotenoids, and tocopherols in homogeneous and heterogeneous aqueous food model systems.

    Science.gov (United States)

    Cardoso, Daniel R; Olsen, Karsten; Skibsted, Leif H

    2007-07-25

    Tocopherols (alpha, beta, gamma, and delta) and Trolox were found to deactivate triplet-excited riboflavin in homogeneous aqueous solution (7:3 v/v tert-butanol/water) with second-order reaction rates close to diffusion control [k2 between 4.8 x 10(8) (delta-tocopherol) and 6.2 x 10(8) L mol(-1) s(-1) (Trolox) at 24.0 +/- 0.2 degrees C] as determined by laser flash photolysis transient absorption spectroscopy. In aqueous buffer (pH 6.4) the rate constant for Trolox was 2.6 x 10(9) L mol(-1) s1 and comparable to the rate constant found for ascorbate (2.0 x 10(9) L mol(-1) s(-1)). The deactivation rate constant was found to be inferior in heterogeneous systems as shown for alpha-tocopherol and Trolox in aqueous Tween-20 emulsion (approximately by a factor of 4 compared to 7:3 v/v tert-butanol/water). Neither beta-carotene (7:3 v/v tert-butanol/water and Tween-20 emulsion), lycopene (7:3 v/v tert-butanol/water), nor crocin (aqueous buffer at pH 6.4, 7:3 v/v tert-butanol/water, and Tween-20 emulsion) showed any quenching on the triplet excited state of riboflavin. Therefore, all carotenoids seem to reduce the formation of triplet-excited riboflavin through an inner-filter effect. Activation parameters were based on the temperature dependence of the triplet-excited deactivation between 15 and 35 degrees C, and the isokinetic behavior, which was found to include purine derivatives previously studied, confirms a common deactivation mechanism with a bimolecular diffusion-controlled encounter with electron (or hydrogen atom) transfer as rate-determining step. DeltaH for deactivation by ascorbic acid, Trolox, and homologue tocopherols (ranging from 18 kJ mol(-1) for Trolox in Tween-20 emulsion to 184 kJ mol(-1) for ascorbic acid in aqueous buffer at pH 6.4) showed a linear dependence on DeltaS (ranging from -19 J mol(-1) K(-1) for Trolox in aqueous buffer at pH 6.4 to +550 J mol(-1) K(-1) for ascorbic acid in aqueous buffer pH 6.4). Among photooxidation products from the

  9. Damage mechanisms in PBT-GF30 under thermo-mechanical cyclic loading

    International Nuclear Information System (INIS)

    Schaaf, A.; De Monte, M.; Hoffmann, C.; Vormwald, M.; Quaresimin, M.

    2014-01-01

    The scope of this paper is the investigation of damage mechanisms at microscopic scale on a short glass fiber reinforced polybutylene terephthalate (PBT-GF30) under thermo-mechanical cyclic loading. In addition the principal mechanisms are verified through micro mechanical FE models. In order to investigate the fatigue behavior of the material both isothermal strain controlled fatigue (ISCF) tests at three different temperatures and thermo-mechanical fatigue (TMF) tests were conducted on plain and notched specimens, manufactured by injection molding. The goal of the work is to determine the damage mechanisms occurring under TMF conditions and to compare them with the mechanisms occurring under ISCF. For this reason fracture surfaces of TMF and ISCF samples loaded at different temperature levels were analyzed using scanning electron microscopy. Furthermore, specimens that failed under TMF were examined on microsections revealing insight into both crack initiation and crack propagation. The findings of this investigation give valuable information about the main damage mechanisms of PBT-GF30 under TMF loading and serve as basis for the development of a TMF life estimation methodology

  10. Survey report on smart-tribo-mechanics; Smart tribo mechanics

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1997-03-01

    Survey results of smart-tribo-mechanics are described. For the smart-tribo-mechanics differing from the conventional tribology, an intelligent system is constructed by making full use of various science and technology ranging from basic to application, to solve problems. Self-diagnosis and self-remediation, active control, passive control, and smart-biotribo-mechanics are typical methods. Electronics, telecommunication, healthcare, and new biotechnology are new and advanced application areas. In these areas, tribology to control and act to the material surface in the atomic and molecular scale should be the key technology. In addition, the smart-tribo-mechanics is expected to be used for sustaining basic industry, such as material, transportation, and life industries. 101 refs., 67 figs., 14 tabs.

  11. Mechanical science

    CERN Document Server

    Bolton, W C

    2013-01-01

    This book gives comprehensive coverage of mechanical science for HNC/HND students taking mechanical engineering courses, including all topics likely to be covered in both years of such courses, as well as for first year undergraduate courses in mechanical engineering. It features 500 problems with answers and 200 worked examples. The third edition includes a new section on power transmission and an appendix on mathematics to help students with the basic notation of calculus and solution of differential equations.

  12. Respiratory mechanics to understand ARDS and guide mechanical ventilation.

    Science.gov (United States)

    Mauri, Tommaso; Lazzeri, Marta; Bellani, Giacomo; Zanella, Alberto; Grasselli, Giacomo

    2017-11-30

    As precision medicine is becoming a standard of care in selecting tailored rather than average treatments, physiological measurements might represent the first step in applying personalized therapy in the intensive care unit (ICU). A systematic assessment of respiratory mechanics in patients with the acute respiratory distress syndrome (ARDS) could represent a step in this direction, for two main reasons. Approach and Main results: On the one hand, respiratory mechanics are a powerful physiological method to understand the severity of this syndrome in each single patient. Decreased respiratory system compliance, for example, is associated with low end expiratory lung volume and more severe lung injury. On the other hand, respiratory mechanics might guide protective mechanical ventilation settings. Improved gravitationally dependent regional lung compliance could support the selection of positive end-expiratory pressure and maximize alveolar recruitment. Moreover, the association between driving airway pressure and mortality in ARDS patients potentially underlines the importance of sizing tidal volume on respiratory system compliance rather than on predicted body weight. The present review article aims to describe the main alterations of respiratory mechanics in ARDS as a potent bedside tool to understand severity and guide mechanical ventilation settings, thus representing a readily available clinical resource for ICU physicians.

  13. Project mechanisms challenges

    International Nuclear Information System (INIS)

    Perthuis, Ch. de

    2005-06-01

    The project mechanism complete the quotas systems concerning the carbon dioxide emissions market. The author explains and discusses these mechanisms and provides a panorama of the existing and developing projects. More specially she brings information on the mechanism of clean developments and renewable energies, the coordinated mechanisms, the agricultural projects, the financing of the projects and the exchange systeme of the New south Wales. (A.L.B.)

  14. Reaction Mechanism of Mycobacterium Tuberculosis Glutamine Synthetase Using Quantum Mechanics/Molecular Mechanics Calculations.

    Science.gov (United States)

    Moreira, Cátia; Ramos, Maria J; Fernandes, Pedro Alexandrino

    2016-06-27

    This paper is devoted to the understanding of the reaction mechanism of mycobacterium tuberculosis glutamine synthetase (mtGS) with atomic detail, using computational quantum mechanics/molecular mechanics (QM/MM) methods at the ONIOM M06-D3/6-311++G(2d,2p):ff99SB//B3LYP/6-31G(d):ff99SB level of theory. The complete reaction undergoes a three-step mechanism: the spontaneous transfer of phosphate from ATP to glutamate upon ammonium binding (ammonium quickly loses a proton to Asp54), the attack of ammonia on phosphorylated glutamate (yielding protonated glutamine), and the deprotonation of glutamine by the leaving phosphate. This exothermic reaction has an activation free energy of 21.5 kcal mol(-1) , which is consistent with that described for Escherichia coli glutamine synthetase (15-17 kcal mol(-1) ). The participating active site residues have been identified and their role and energy contributions clarified. This study provides an insightful atomic description of the biosynthetic reaction that takes place in this enzyme, opening doors for more accurate studies for developing new anti-tuberculosis therapies. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Mechanical and dynamic mechanical behaviour of novel glass ...

    Indian Academy of Sciences (India)

    M Rajesh

    the intra-ply woven fabric hybridization enhances impact and damping properties of the composite ... Keywords. Intra-ply hybrid; natural fibre; mechanical properties; dynamic mechanical analysis; vibration; .... analysis test is conducted in nitrogen environment over a ..... Mnson J A and Jolliet O 2001 Life cycle assessment of.

  16. Mechanical Ventilation

    Science.gov (United States)

    ... ventilation is a life support treatment. A mechanical ventilator is a machine that helps people breathe when ... to breathe enough on their own. The mechanical ventilator is also called a ventilator , respirator, or breathing ...

  17. Mechanisms and mechanics of porosity formation in ductile iron castings

    Directory of Open Access Journals (Sweden)

    M. Perzyk

    2007-12-01

    Full Text Available Shrinkage defects in ductile iron castings can be of two basic types: shrinkage cavities associated with the liquid contraction prior to the expansion period of the iron as well as the porosity, which may appear even if the liquid shrinkage is fully compensated. In the present paper two possible mechanisms of the porosity are presented and analyzed. The first one is the Karsay’s mechanism based on the secondary shrinkage concept. The second one is the mechanism acting during the expansion period of the iron, first suggested by Ohnaka and co-authors and essentially modified by the present authors. The mechanical interactions between casting and mould are determined for the both mechanisms. Their analysis leads to the conclusion, that porosity forms during expansion period of the melt. The direct cause is the negative pressure which appears in the central part of the casting due to the differences in expansion coefficients of the fast cooling surface layer and slow cooling inner region. Observations concerning feeding behavior of ductile iron castings, based on this mechanism, agree well with industrial practice. The secondary shrinkage is not only needless to induce the porosity, but the corresponding mechanism of its occurrence, proposed by Karsay, does not seem to be valid.

  18. Handbook of compliant mechanisms

    CERN Document Server

    Howell, Larry L; Olsen, Brian M

    2013-01-01

    A fully illustrated reference book giving an easy-to-understand introduction to compliant mechanisms A broad compilation of compliant mechanisms to give inspiration and guidance to those interested in using compliant mechanisms in their designs, the Handbook of Compliant Mechanisms includes graphics and descriptions of many compliant mechanisms. It comprises an extensive categorization of devices that can be used to help readers identify compliant mechanisms related to their application. It also provides chapters on the basic background in compliant mechanisms, the categories o

  19. Deformation mechanisms in ferritic/martensitic steels and the impact on mechanical design

    International Nuclear Information System (INIS)

    Ghoniem, Nasr M.; Po, Giacomo; Sharafat, Shahram

    2013-01-01

    Structural steels for nuclear applications have undergone rapid development during the past few decades, thanks to a combination of trial-and-error, mechanism-based optimization, and multiscale modeling approaches. Deformation mechanisms are shown to be intimately related to mechanical design via dominant plastic deformation modes. Because mechanical design rules are mostly based on failure modes associated with plastic strain damage accumulation, we present here the fundamental deformation mechanisms for Ferritic/Martensitic (F/M) steels, and delineate their operational range of temperature and stress. The connection between deformation mechanisms, failure modes, and mechanical design is shown through application of design rules. A specific example is given for the alloy F82H utilized in the design of a Test Blanket Module (TBM) in the International Thermonuclear Experimental Reactor (ITER), where several constitutive equations are developed for design-related mechanical properties

  20. Deformation mechanisms in ferritic/martensitic steels and the impact on mechanical design

    Energy Technology Data Exchange (ETDEWEB)

    Ghoniem, Nasr M., E-mail: ghoniem@seas.ucla.edu; Po, Giacomo; Sharafat, Shahram

    2013-10-15

    Structural steels for nuclear applications have undergone rapid development during the past few decades, thanks to a combination of trial-and-error, mechanism-based optimization, and multiscale modeling approaches. Deformation mechanisms are shown to be intimately related to mechanical design via dominant plastic deformation modes. Because mechanical design rules are mostly based on failure modes associated with plastic strain damage accumulation, we present here the fundamental deformation mechanisms for Ferritic/Martensitic (F/M) steels, and delineate their operational range of temperature and stress. The connection between deformation mechanisms, failure modes, and mechanical design is shown through application of design rules. A specific example is given for the alloy F82H utilized in the design of a Test Blanket Module (TBM) in the International Thermonuclear Experimental Reactor (ITER), where several constitutive equations are developed for design-related mechanical properties.

  1. Electrical characterizations of biomimetic molecular layers on gold and silicon substrates

    International Nuclear Information System (INIS)

    Chilcott, T C; Wong, E L S; Coster, H G L; Böcking, T

    2008-01-01

    Electrical impedance technology was used to characterize DNA recognition in a monolayer containing single-stranded DNA probes immobilized on a gold substrate using thiol self-assembly chemistry. Recognition of targeted complementary DNA was principally correlated with an eight-fold increase in the conductance of the monolayer and attributed to electron conduction through double helices formed upon the binding of the DNA targets to the probes. The high recognitive sensitivity was possible without the use of the redox labels or large bias voltages required for recognition using cyclic and Osteryoung square wave voltammetry. The impedance technology also provided atomic resolution of a hybrid bimolecular lipid membrane formed by deposition of a phospholipid:cholesterol monolayer onto a hydrophobic alkyl monolayer covalently attached to a silicon substrate via silicon–carbon bonds. Atomic resolution was achieved through preparation of membranes on surfaces approaching atomic flatness and the performance of impedance measurements over precisely defined areas of the surface in contact with solutions. Principally capacitive properties distinguished between the immobilized (octadecyl) and more fluidic (lipid:cholesterol) leaflets of the hybrid membrane. The lipid:cholesterol leaflets were structurally similar to those leaflets in free-standing bimolecular lipid membranes. The hybrid membrane therefore provides a highly stable and physiologically relevant surface for studying biomolecular interactions with membrane surfaces

  2. Nongeminate radiative recombination of free charges in cation-exchanged PbS quantum dot films

    Energy Technology Data Exchange (ETDEWEB)

    Marshall, Ashley R. [National Renewable Energy Laboratory, 15013 Denver West Pkwy., Golden, CO 80401 (United States); Department of Chemistry and Biochemistry, University of Colorado, Boulder, CO 80309 (United States); Beard, Matthew C.; Johnson, Justin C. [National Renewable Energy Laboratory, 15013 Denver West Pkwy., Golden, CO 80401 (United States)

    2016-06-01

    Highlights: • Photoluminescence and transient absorption are used to probe PbS QD films. • Cation-exchanged PbS QDs show room-temperature PL emission. • Bimolecular recombination is shown for the first time in coupled, PbS QD films. - Abstract: Using photoluminescence (PL) spectroscopy we explore the radiative recombination pathways in PbS quantum dots (QDs) synthesized by two methods. We compare conventionally synthesized PbS from a PbO precursor to PbS synthesized using cation-exchange from CdS QDs. We show that strongly coupled films of PbS QDs from the cation-exchange luminesce with significant efficiency at room temperature. This is in stark contrast to conventional PbS QDs, which have exceedingly weak room temperature emission. Moreover, the power dependence of the emission is quadratic, indicating bimolecular radiative recombination that is reasonably competitive with trap-assisted recombination, a feature previously unreported in coupled PbS QD films. We interpret these results in terms of a greatly reduced defect concentration for cation-exchanged QDs that mitigates the influence of trap-assisted recombination. Cation-exchanged QDs have recently been employed in highly efficient and air-stable lead chalcogenide QD devices, and the reduced number of trap states inferred here may lead to improved current collection and higher open circuit voltage.

  3. Confining Domains Lead to Reaction Bursts: Reaction Kinetics in the Plasma Membrane

    Science.gov (United States)

    Kalay, Ziya; Fujiwara, Takahiro K.; Kusumi, Akihiro

    2012-01-01

    Confinement of molecules in specific small volumes and areas within a cell is likely to be a general strategy that is developed during evolution for regulating the interactions and functions of biomolecules. The cellular plasma membrane, which is the outermost membrane that surrounds the entire cell, was considered to be a continuous two-dimensional liquid, but it is becoming clear that it consists of numerous nano-meso-scale domains with various lifetimes, such as raft domains and cytoskeleton-induced compartments, and membrane molecules are dynamically trapped in these domains. In this article, we give a theoretical account on the effects of molecular confinement on reversible bimolecular reactions in a partitioned surface such as the plasma membrane. By performing simulations based on a lattice-based model of diffusion and reaction, we found that in the presence of membrane partitioning, bimolecular reactions that occur in each compartment proceed in bursts during which the reaction rate is sharply and briefly increased even though the asymptotic reaction rate remains the same. We characterized the time between reaction bursts and the burst amplitude as a function of the model parameters, and discussed the biological significance of the reaction bursts in the presence of strong inhibitor activity. PMID:22479350

  4. Confining domains lead to reaction bursts: reaction kinetics in the plasma membrane.

    Directory of Open Access Journals (Sweden)

    Ziya Kalay

    Full Text Available Confinement of molecules in specific small volumes and areas within a cell is likely to be a general strategy that is developed during evolution for regulating the interactions and functions of biomolecules. The cellular plasma membrane, which is the outermost membrane that surrounds the entire cell, was considered to be a continuous two-dimensional liquid, but it is becoming clear that it consists of numerous nano-meso-scale domains with various lifetimes, such as raft domains and cytoskeleton-induced compartments, and membrane molecules are dynamically trapped in these domains. In this article, we give a theoretical account on the effects of molecular confinement on reversible bimolecular reactions in a partitioned surface such as the plasma membrane. By performing simulations based on a lattice-based model of diffusion and reaction, we found that in the presence of membrane partitioning, bimolecular reactions that occur in each compartment proceed in bursts during which the reaction rate is sharply and briefly increased even though the asymptotic reaction rate remains the same. We characterized the time between reaction bursts and the burst amplitude as a function of the model parameters, and discussed the biological significance of the reaction bursts in the presence of strong inhibitor activity.

  5. An Optical Fiber Read Out Method for a Reflective Microcantilever Biosensor

    Directory of Open Access Journals (Sweden)

    Feng Wen

    2013-03-01

    Full Text Available An effective optical read out approach based on fiber reflective is presented to detect bends of a biomaterial microcantilever. The microcantilever was fabricated on single crystalline SOI wafer using a series of side definitions and backside wet/dry etchings. A Cr/Au layer with 30 nm Cr and 50 nm Au layer was deposited for the immobilized of bimolecular on the cantilever surface and for reflecting the light back into the fiber, the different light intensities means different bimolecular concentrations. The noncoherent light source is a super luminescent LED. Gradient index lens as a collimator and 50:50 optical coupler and signal modefiber was used to transmit light. Two PINFETs were used to convert the reflecting the light intensities and the light sources into electronic signals, two ADCs convert the signal into digital signals, a MPU was used to eliminate the fluctuation of the light source error. The method can has got high sensitivity is 6507.59 mV/um. Though the experiment, the cantilever biosensor can detect glucose, measurement results clearly demonstrate that the output voltage induced by the microcantilevers bending is proportional to the glucose concentrations and the sensitivity is up to 0.1V/mM, which is enough for glucose real-time trace detection.

  6. Rate kernel theory for pseudo-first-order kinetics of diffusion-influenced reactions and application to fluorescence quenching kinetics.

    Science.gov (United States)

    Yang, Mino

    2007-06-07

    Theoretical foundation of rate kernel equation approaches for diffusion-influenced chemical reactions is presented and applied to explain the kinetics of fluorescence quenching reactions. A many-body master equation is constructed by introducing stochastic terms, which characterize the rates of chemical reactions, into the many-body Smoluchowski equation. A Langevin-type of memory equation for the density fields of reactants evolving under the influence of time-independent perturbation is derived. This equation should be useful in predicting the time evolution of reactant concentrations approaching the steady state attained by the perturbation as well as the steady-state concentrations. The dynamics of fluctuation occurring in equilibrium state can be predicted by the memory equation by turning the perturbation off and consequently may be useful in obtaining the linear response to a time-dependent perturbation. It is found that unimolecular decay processes including the time-independent perturbation can be incorporated into bimolecular reaction kinetics as a Laplace transform variable. As a result, a theory for bimolecular reactions along with the unimolecular process turned off is sufficient to predict overall reaction kinetics including the effects of unimolecular reactions and perturbation. As the present formulation is applied to steady-state kinetics of fluorescence quenching reactions, the exact relation between fluorophore concentrations and the intensity of excitation light is derived.

  7. Effects of Bimolecular Recombination on Impedance Spectra in Organic Semiconductors: Analytical Approach.

    Science.gov (United States)

    Takata, Masashi; Takagi, Kenichiro; Nagase, Takashi; Kobayashi, Takashi; Naito, Hiroyoshi

    2016-04-01

    An analytical expression for impedance spectra in the case of double injection (both electrons and holes are injected into an organic semiconductor thin film) has been derived from the basic transport equations (the current density equation, the continuity equation and the Possion's equation). Capacitance-frequency characteristics calculated from the analytical expression have been examined at different recombination constants and different values of mobility balance defined by a ratio of electron mobility to hole mobility. Negative capacitance appears when the recombination constant is lower than the Langevin recombination constant and when the value of the mobility balance approaches unity. These results are consistent with the numerical results obtained by a device simulator (Atlas, Silvaco).

  8. Entropy in bimolecular simulations: A comprehensive review of atomic fluctuations-based methods.

    Science.gov (United States)

    Kassem, Summer; Ahmed, Marawan; El-Sheikh, Salah; Barakat, Khaled H

    2015-11-01

    Entropy of binding constitutes a major, and in many cases a detrimental, component of the binding affinity in biomolecular interactions. While the enthalpic part of the binding free energy is easier to calculate, estimating the entropy of binding is further more complicated. A precise evaluation of entropy requires a comprehensive exploration of the complete phase space of the interacting entities. As this task is extremely hard to accomplish in the context of conventional molecular simulations, calculating entropy has involved many approximations. Most of these golden standard methods focused on developing a reliable estimation of the conformational part of the entropy. Here, we review these methods with a particular emphasis on the different techniques that extract entropy from atomic fluctuations. The theoretical formalisms behind each method is explained highlighting its strengths as well as its limitations, followed by a description of a number of case studies for each method. We hope that this brief, yet comprehensive, review provides a useful tool to understand these methods and realize the practical issues that may arise in such calculations. Copyright © 2015 Elsevier Inc. All rights reserved.

  9. Robot Mechanisms

    CERN Document Server

    Lenarcic, Jadran; Stanišić, Michael M

    2013-01-01

    This book provides a comprehensive introduction to the area of robot mechanisms, primarily considering industrial manipulators and humanoid arms. The book is intended for both teaching and self-study. Emphasis is given to the fundamentals of kinematic analysis and the design of robot mechanisms. The coverage of topics is untypical. The focus is on robot kinematics. The book creates a balance between theoretical and practical aspects in the development and application of robot mechanisms, and includes the latest achievements and trends in robot science and technology.

  10. Mechanical efficiency of two commercial lever-propulsion mechanisms for manual wheelchair locomotion.

    Science.gov (United States)

    Lui, Jordon; MacGillivray, Megan K; Sheel, A William; Jeyasurya, Jeswin; Sadeghi, Mahsa; Sawatzky, Bonita Jean

    2013-01-01

    The purpose of this study was to (1) evaluate the mechanical efficiency (ME) of two commercially available lever-propulsion mechanisms for wheelchairs and (2) compare the ME of lever propulsion with hand rim propulsion within the same wheelchair. Of the two mechanisms, one contained a torsion spring while the other used a roller clutch design. We hypothesized that the torsion spring mechanism would increase the ME of propulsion due to a passive recovery stroke enabled by the mechanism. Ten nondisabled male participants with no prior manual wheeling experience performed submaximal exercise tests using both lever-propulsion mechanisms and hand rim propulsion on two different wheelchairs. Cardiopulmonary parameters including oxygen uptake (VO2), heart rate (HR), and energy expenditure (En) were determined. Total external power (Pext) was measured using a drag test protocol. ME was determined by the ratio of Pext to En. Results indicated no significant effect of lever-propulsion mechanism for all physiological measures tested. This suggests that the torsion spring did not result in a physiological benefit compared with the roller clutch mechanism. However, both lever-propulsion mechanisms showed decreased VO2 and HR and increased ME (as a function of slope) compared with hand rim propulsion (p propulsion mechanisms tested are more mechanically efficient than conventional hand rim propulsion, especially when slopes are encountered.

  11. Verifiably Truthful Mechanisms

    DEFF Research Database (Denmark)

    Branzei, Simina; Procaccia, Ariel D.

    2015-01-01

    the computational sense). Our approach involves three steps: (i) specifying the structure of mechanisms, (ii) constructing a verification algorithm, and (iii) measuring the quality of verifiably truthful mechanisms. We demonstrate this approach using a case study: approximate mechanism design without money...

  12. Atomistic insight into the catalytic mechanism of glycosyltransferases by combined quantum mechanics/molecular mechanics (QM/MM) methods.

    Science.gov (United States)

    Tvaroška, Igor

    2015-02-11

    Glycosyltransferases catalyze the formation of glycosidic bonds by assisting the transfer of a sugar residue from donors to specific acceptor molecules. Although structural and kinetic data have provided insight into mechanistic strategies employed by these enzymes, molecular modeling studies are essential for the understanding of glycosyltransferase catalyzed reactions at the atomistic level. For such modeling, combined quantum mechanics/molecular mechanics (QM/MM) methods have emerged as crucial. These methods allow the modeling of enzymatic reactions by using quantum mechanical methods for the calculation of the electronic structure of the active site models and treating the remaining enzyme environment by faster molecular mechanics methods. Herein, the application of QM/MM methods to glycosyltransferase catalyzed reactions is reviewed, and the insight from modeling of glycosyl transfer into the mechanisms and transition states structures of both inverting and retaining glycosyltransferases are discussed. Copyright © 2014 Elsevier Ltd. All rights reserved.

  13. Analytical mechanics

    CERN Document Server

    Lemos, Nivaldo A

    2018-01-01

    Analytical mechanics is the foundation of many areas of theoretical physics including quantum theory and statistical mechanics, and has wide-ranging applications in engineering and celestial mechanics. This introduction to the basic principles and methods of analytical mechanics covers Lagrangian and Hamiltonian dynamics, rigid bodies, small oscillations, canonical transformations and Hamilton–Jacobi theory. This fully up-to-date textbook includes detailed mathematical appendices and addresses a number of advanced topics, some of them of a geometric or topological character. These include Bertrand's theorem, proof that action is least, spontaneous symmetry breakdown, constrained Hamiltonian systems, non-integrability criteria, KAM theory, classical field theory, Lyapunov functions, geometric phases and Poisson manifolds. Providing worked examples, end-of-chapter problems, and discussion of ongoing research in the field, it is suitable for advanced undergraduate students and graduate students studying analyt...

  14. Fracture mechanics

    CERN Document Server

    Perez, Nestor

    2017-01-01

    The second edition of this textbook includes a refined presentation of concepts in each chapter, additional examples; new problems and sections, such as conformal mapping and mechanical behavior of wood; while retaining all the features of the original book. The material included in this book is based upon the development of analytical and numerical procedures pertinent to particular fields of linear elastic fracture mechanics (LEFM) and plastic fracture mechanics (PFM), including mixed-mode-loading interaction. The mathematical approach undertaken herein is coupled with a brief review of several fracture theories available in cited references, along with many color images and figures. Dynamic fracture mechanics is included through the field of fatigue and Charpy impact testing. Explains computational and engineering approaches for solving crack-related problems using straightforward mathematics that facilitate comprehension of the physical meaning of crack growth processes; Expands computational understandin...

  15. Introductory Education for Mechanical Engineering by Exercise in Mechanical Disassembly

    Science.gov (United States)

    Matsui, Yoshio; Asakawa, Naoki; Iwamori, Satoru

    An introductory program “Exercise for engineers in mechanical disassembly” is an exercise that ten students of every team disassemble a motor scooter to the components and then assemble again to the initial form in 15 weeks. The purpose of this program is to introduce mechanical engineering by touching the real machine and learning how it is composed from various mechanical parts to the students at the early period after the entrance into the university. Additional short lectures by young teachers and a special lecture by a top engineer in the industry encourage the students to combine the actual machine and the mechanical engineering subjects. Furthermore, various educations such as group leader system, hazard prediction training, parts filing are included in this program. As a result, students recognize the importance of the mechanical engineering study and the way of group working.

  16. Quantum mechanics

    International Nuclear Information System (INIS)

    Rae, A.I.M.

    1981-01-01

    This book, based on a thirty lecture course given to students at the beginning of their second year, covers the quantum mechanics required by physics undergraduates. Early chapters deal with wave mechanics, including a discussion of the energy states of the hydrogen atom. These are followed by a more formal development of the theory, leading to a discussion of some advanced applications and an introduction to the conceptual problems associated with quantum measurement theory. Emphasis is placed on the fundamentals of quantum mechanics. Problems are included at the end of each chapter. (U.K.)

  17. Quantum mechanics

    CERN Document Server

    Powell, John L

    2015-01-01

    Suitable for advanced undergraduates, this thorough text focuses on the role of symmetry operations and the essentially algebraic structure of quantum-mechanical theory. Based on courses in quantum mechanics taught by the authors, the treatment provides numerous problems that require applications of theory and serve to supplement the textual material.Starting with a historical introduction to the origins of quantum theory, the book advances to discussions of the foundations of wave mechanics, wave packets and the uncertainty principle, and an examination of the Schrödinger equation that includ

  18. Fractional quantum mechanics

    CERN Document Server

    Laskin, Nick

    2018-01-01

    Fractional quantum mechanics is a recently emerged and rapidly developing field of quantum physics. This is the first monograph on fundamentals and physical applications of fractional quantum mechanics, written by its founder. The fractional Schrödinger equation and the fractional path integral are new fundamental physical concepts introduced and elaborated in the book. The fractional Schrödinger equation is a manifestation of fractional quantum mechanics. The fractional path integral is a new mathematical tool based on integration over Lévy flights. The fractional path integral method enhances the well-known Feynman path integral framework. Related topics covered in the text include time fractional quantum mechanics, fractional statistical mechanics, fractional classical mechanics and the α-stable Lévy random process. The book is well-suited for theorists, pure and applied mathematicians, solid-state physicists, chemists, and others working with the Schrödinger equation, the path integral technique...

  19. Exciton Transport Simulations in Phenyl Cored Thiophene Dendrimers

    Science.gov (United States)

    Kim, Kwiseon; Erkan Kose, Muhammet; Graf, Peter; Kopidakis, Nikos; Rumbles, Garry; Shaheen, Sean E.

    2009-03-01

    Phenyl cored 3-arm and 4-arm thiophene dendrimers are promising materials for use in photovoltaic devices. It is important to understand the energy transfer mechanisms in these molecules to guide the synthesis of novel dendrimers with improved efficiency. A method is developed to estimate the exciton diffusion lengths for the dendrimers and similar chromophores in amorphous films. The approach exploits Fermi's Golden Rule to estimate the energy transfer rates for an ensemble of bimolecular complexes in random orientations. Using Poisson's equation to evaluate Coulomb integrals led to efficient calculation of excitonic couplings between the transition densities. Monte-Carlo simulations revealed the dynamics of energy transport in the dendrimers. Experimental exciton diffusion lengths of the dendrimers range 10 ˜ 20 nm, increasing with the size of the dendrimer. Simulated diffusion lengths correlate well with experiments. The chemical structure of the chromophore, the shape of the transition densities and the exciton lifetime are found to be the most important factors that determine the exciton diffusion length in amorphous films.

  20. B10(n,α)Li7 irradiation effects on high impact polystyrene

    International Nuclear Information System (INIS)

    Gupta, M.C.; Bansod, V.P.

    1984-01-01

    Irradiation effects of B 10 (n,α)Li 7 charged particles on high impact polystyrene were compared with those of Co 60 γ-rays, from the viewpoint of linear energy transfer (LET). For irradiation in air, the G values of crosslinks and main-chain scissions, G(X) and G(S) are 0.018 and 0.06, respectively, for γ-rays of low LET (ca. 0.22 eV/nm). Charged particles [B 10 (n,α)Li 7 ] of high LET (ca. 280 eV/nm) increase the G(X) value to 0.15 but G(S) is not much affected. All these findings are explained qualitatively by a difference in the distribution of energy deposition and the mechanism involving the competition between the deactivation of an excited molecule by the collision with ground state molecules and the macroradical formation by the bimolecular reaction of the excited molecules. These excited molecules in HIPS might be produced more closely to one another by charged particles than by γ-rays. (author)

  1. Why quantum mechanics?

    International Nuclear Information System (INIS)

    Landsberg, P.T.

    1988-01-01

    It is suggested that an oversight occurred in classical mechanics when time-derivatives of observables were treated on the same footing as the undifferentiated observables. Removal of this oversight points in the direction of quantum mechanics. Additional light is thrown on uncertainty relations and on quantum mechanics, as a possible form of a subtle statistical mechanics, by the formulation of a classical uncertainty relation for a very simple model. The existence of universal motion, i.e., of zero-point energy, is lastly made plausible in terms of a gravitational constant which is time-dependent. By these three considerations an attempt is made to link classical and quantum mechanics together more firmly, thus giving a better understanding of the latter

  2. Advances in Applied Mechanics

    OpenAIRE

    2013-01-01

    Advances in Applied Mechanics draws together recent significant advances in various topics in applied mechanics. Published since 1948, Advances in Applied Mechanics aims to provide authoritative review articles on topics in the mechanical sciences, primarily of interest to scientists and engineers working in the various branches of mechanics, but also of interest to the many who use the results of investigations in mechanics in various application areas, such as aerospace, chemical, civil, en...

  3. Dynamics of anion-molecule reactions at low energy

    International Nuclear Information System (INIS)

    Mikosch, J.

    2007-11-01

    Anion-molecule reactions must find their way through deeply bound entrance and exit channel complexes separated by a central barrier. This results in low reaction rates and rich dynamics since direct pathways compete with the formation of transient intermediates. In this thesis we examine the probability of proton transfer to a small anion and transient lifetimes of a thermoneutral bimolecular nucleophilic substitution (S N 2) reaction at well defined variable temperature down to 8 Kelvin in a multipole trap. The observed strong inverse temperature dependence is attributed to the deficit of available quantum states in the entrance channel at decreasing temperature. Furthermore we investigate scattering dynamics of S N 2 reactions at defined relative energy between 0.4 and 10 eV by crossed beam slice imaging. A weakly exothermic reaction with high central barrier proceeds via an indirect, complex-mediated mechanism at low relative energies featuring high internal product excitation in excellent quantitative agreement with a statistical model. In contrast, direct backward scattering prevails for higher energies with product velocities close to the kinematical cutoff. For a strongly exothermic reaction, competing S N 2-, dihalide- and proton transfer-channels are explored which proceed by complex mediation for low energy and various rebound-, grazing- and collision induced bond rupture-mechanisms at higher energy. From our data and a collaboration with theory we identify a new indirect roundabout S N 2 mechanism involving CH 3 -rotation. (orig.)

  4. Dynamics of anion-molecule reactions at low energy

    Energy Technology Data Exchange (ETDEWEB)

    Mikosch, J.

    2007-11-15

    Anion-molecule reactions must find their way through deeply bound entrance and exit channel complexes separated by a central barrier. This results in low reaction rates and rich dynamics since direct pathways compete with the formation of transient intermediates. In this thesis we examine the probability of proton transfer to a small anion and transient lifetimes of a thermoneutral bimolecular nucleophilic substitution (S{sub N}2) reaction at well defined variable temperature down to 8 Kelvin in a multipole trap. The observed strong inverse temperature dependence is attributed to the deficit of available quantum states in the entrance channel at decreasing temperature. Furthermore we investigate scattering dynamics of S{sub N}2 reactions at defined relative energy between 0.4 and 10 eV by crossed beam slice imaging. A weakly exothermic reaction with high central barrier proceeds via an indirect, complex-mediated mechanism at low relative energies featuring high internal product excitation in excellent quantitative agreement with a statistical model. In contrast, direct backward scattering prevails for higher energies with product velocities close to the kinematical cutoff. For a strongly exothermic reaction, competing S{sub N}2-, dihalide- and proton transfer-channels are explored which proceed by complex mediation for low energy and various rebound-, grazing- and collision induced bond rupture-mechanisms at higher energy. From our data and a collaboration with theory we identify a new indirect roundabout S{sub N}2 mechanism involving CH{sub 3}-rotation. (orig.)

  5. ANALYSIS OF THE MECHANICAL STRENGTH OF A DRIVING MECHANISM CALLED SHOCK

    Directory of Open Access Journals (Sweden)

    Dan ILINCIOIU

    2015-05-01

    Full Text Available It evaluates the maximum static and dynamic stresses produced in the elements of a quadrilateral mechanism transporting a vehicle in the storage in an urban park. Determine multiplier shock hazard if the mechanism freezes and increases mechanical stress.

  6. Enabling nucleophilic substitution reactions of activated alkyl fluorides through hydrogen bonding.

    Science.gov (United States)

    Champagne, Pier Alexandre; Pomarole, Julien; Thérien, Marie-Ève; Benhassine, Yasmine; Beaulieu, Samuel; Legault, Claude Y; Paquin, Jean-François

    2013-05-03

    It was discovered that the presence of water as a cosolvent enables the reaction of activated alkyl fluorides for bimolecular nucleophilic substitution reactions. DFT calculations show that activation proceeds through stabilization of the transition structure by a stronger F···H2O interaction and diminishing C-F bond elongation, and not simple transition state electrostatic stabilization. Overall, the findings put forward a distinct strategy for C-F bond activation through H-bonding.

  7. Calorimetric investigation on mechanically activated storage energy mechanism of sphalerite and pyrite

    International Nuclear Information System (INIS)

    Xiao Zhongliang; Chen Qiyuan; Yin Zhoulan; Hu Huiping; Wu Daoxin

    2005-01-01

    The structural changes of mechanically activated sphalerite and pyrite under different grinding conditions were determined by X-ray powder diffraction (XRD), laser particle size analyzer and elemental analysis. The storage energy of mechanically activated sphalerite and pyrite was measured by a calorimetric method. A thermochemical cycle was designed so that mechanically activated and non-activated minerals reached the same final state when dissolved in the same oxidizing solvent. The results show that the storage energy of mechanically activated sphalerite and pyrite rises with increased in grinding time, and reaches a maximum after a certain grinding period. The storage energy of mechanically activated pyrite decreases when heated under inert atmosphere. The storage energy of mechanically activated sphalerite and pyrite remains constant when treated below 573 K under inert atmosphere. The percentage of the storage energy caused by surface area increase during mechanical activation decreases with increasing grinding time. These results support our opinion that the mechanically activated storage energy of sphalerite is closely related to lattice distortions, and the mechanically activated storage energy of pyrite is mainly caused by the formation of reactive sites on the surface

  8. Quantum opto-mechanics with micromirrors : combining nano-mechanics with quantum optics

    International Nuclear Information System (INIS)

    Groeblacher, S.

    2010-01-01

    This work describes more than four years of research on the effects of the radiation-pressure force of light on macroscopic mechanical structures. The basic system studied here is a mechanical oscillator that is highly reflective and part of an optical resonator. It interacts with the optical cavity mode via the radiation-pressure force. Both the dynamics of the mechanical oscillation and the properties of the light field are modified through this interaction. In our experiments we use quantum optical tools (such as homodyning and down-conversion) with the goal of ultimately showing quantum behavior of the mechanical center of mass motion. In this thesis we present several experiments that pave the way towards this goal and when combined should allow the demonstration of the envisioned quantum phenomena, including entanglement, teleportation and Schroeodinger cat states. The study of quantum behavior of truly macroscopic systems is a long outstanding goal, which will help to answer some of the most fundamental questions in quantum physics today: Why is the world around us classical and not quantum? Is there a size- or mass-limit to systems for them to behave according to quantum mechanics? Is quantum theory complete or do we have to extend it to include mechanisms such as decoherence? Can we use the quantum nature of macroscopic objects to, for example, improve the measurement precision of classical apparatuses? The experiments discussed in this thesis include the very first passive radiation-pressure cooling of a mechanical oscillator in a cryogenic optical resonator, as well as the experimental demonstration of radiation-pressure cooling close to the mechanical quantum ground state. Cooling of the mechanical motion is an important pre-condition for observing quantum effects of the mechanical oscillator. In another experiment, we have demonstrated that we are able to enter the strong-coupling regime of the optomechanical system a regime where coherent energy

  9. Quantum mechanics/coarse-grained molecular mechanics (QM/CG-MM).

    Science.gov (United States)

    Sinitskiy, Anton V; Voth, Gregory A

    2018-01-07

    Numerous molecular systems, including solutions, proteins, and composite materials, can be modeled using mixed-resolution representations, of which the quantum mechanics/molecular mechanics (QM/MM) approach has become the most widely used. However, the QM/MM approach often faces a number of challenges, including the high cost of repetitive QM computations, the slow sampling even for the MM part in those cases where a system under investigation has a complex dynamics, and a difficulty in providing a simple, qualitative interpretation of numerical results in terms of the influence of the molecular environment upon the active QM region. In this paper, we address these issues by combining QM/MM modeling with the methodology of "bottom-up" coarse-graining (CG) to provide the theoretical basis for a systematic quantum-mechanical/coarse-grained molecular mechanics (QM/CG-MM) mixed resolution approach. A derivation of the method is presented based on a combination of statistical mechanics and quantum mechanics, leading to an equation for the effective Hamiltonian of the QM part, a central concept in the QM/CG-MM theory. A detailed analysis of different contributions to the effective Hamiltonian from electrostatic, induction, dispersion, and exchange interactions between the QM part and the surroundings is provided, serving as a foundation for a potential hierarchy of QM/CG-MM methods varying in their accuracy and computational cost. A relationship of the QM/CG-MM methodology to other mixed resolution approaches is also discussed.

  10. Quantum mechanics/coarse-grained molecular mechanics (QM/CG-MM)

    Science.gov (United States)

    Sinitskiy, Anton V.; Voth, Gregory A.

    2018-01-01

    Numerous molecular systems, including solutions, proteins, and composite materials, can be modeled using mixed-resolution representations, of which the quantum mechanics/molecular mechanics (QM/MM) approach has become the most widely used. However, the QM/MM approach often faces a number of challenges, including the high cost of repetitive QM computations, the slow sampling even for the MM part in those cases where a system under investigation has a complex dynamics, and a difficulty in providing a simple, qualitative interpretation of numerical results in terms of the influence of the molecular environment upon the active QM region. In this paper, we address these issues by combining QM/MM modeling with the methodology of "bottom-up" coarse-graining (CG) to provide the theoretical basis for a systematic quantum-mechanical/coarse-grained molecular mechanics (QM/CG-MM) mixed resolution approach. A derivation of the method is presented based on a combination of statistical mechanics and quantum mechanics, leading to an equation for the effective Hamiltonian of the QM part, a central concept in the QM/CG-MM theory. A detailed analysis of different contributions to the effective Hamiltonian from electrostatic, induction, dispersion, and exchange interactions between the QM part and the surroundings is provided, serving as a foundation for a potential hierarchy of QM/CG-MM methods varying in their accuracy and computational cost. A relationship of the QM/CG-MM methodology to other mixed resolution approaches is also discussed.

  11. Transition from the mechanics of material points to the mechanics of structured particles

    Science.gov (United States)

    Somsikov, V. M.

    2016-01-01

    In this paper, necessity of creation of mechanics of structured particles is discussed. The way to create this mechanics within the laws of classical mechanics with the use of energy equation is shown. The occurrence of breaking of time symmetry within the mechanics of structured particles is shown, as well as the introduction of concept of entropy in the framework of classical mechanics. The way to create the mechanics of non-equilibrium systems in the thermodynamic approach is shown. It is also shown that the use of hypothesis of holonomic constraints while deriving the canonical Lagrange equation made it impossible to describe irreversible dynamics. The difference between the mechanics of structured particles and the mechanics of material points is discussed. It is also shown that the matter is infinitely divisible according to the laws of classical mechanics.

  12. Schrodinger's mechanics interpretation

    CERN Document Server

    Cook, David B

    2018-01-01

    The interpretation of quantum mechanics has been in dispute for nearly a century with no sign of a resolution. Using a careful examination of the relationship between the final form of classical particle mechanics (the Hamilton–Jacobi Equation) and Schrödinger's mechanics, this book presents a coherent way of addressing the problems and paradoxes that emerge through conventional interpretations.Schrödinger's Mechanics critiques the popular way of giving physical interpretation to the various terms in perturbation theory and other technologies and places an emphasis on development of the theory and not on an axiomatic approach. When this interpretation is made, the extension of Schrödinger's mechanics in relation to other areas, including spin, relativity and fields, is investigated and new conclusions are reached.

  13. Automotive Mechanics.

    Science.gov (United States)

    Linder, Ralph C.; And Others

    This curriculum guide, which was validated by vocational teachers and mechanics in the field, describes the competencies needed by entry-level automotive mechanics. This guide lists 15 competencies; for each competency, various tasks with their performance objective, student learning experiences, suggested instructional techniques, instructional…

  14. Detailed characterizations of a Comparative Reactivity Method (CRM) instrument: experiments vs. modelling

    Science.gov (United States)

    Michoud, V.; Hansen, R. F.; Locoge, N.; Stevens, P. S.; Dusanter, S.

    2015-04-01

    simple chemical mechanism, taking into account the inorganic chemistry from IUPAC 2001 and a simple organic chemistry scheme including only a generic RO2 compounds for all oxidized organic trace gases; and (2) a more exhaustive chemical mechanism, based on the Master Chemical Mechanism (MCM), including the chemistry of the different trace gases used during laboratory experiments. Both mechanisms take into account self- and cross-reactions of radical species. The simulations using these mechanisms allow reproducing the magnitude of the corrections needed to account for NO interferences and a deviation from pseudo first-order kinetics, as well as their dependence on the Pyrrole-to-OH ratio and on bimolecular reaction rate constants of trace gases. The reasonable agreement found between laboratory experiments and model simulations gives confidence in the parameterizations proposed to correct the Total OH reactivity measured by CRM. However, it must be noted that the parameterizations presented in this paper are suitable for the CRM instrument used during the laboratory characterization and may be not appropriate for other CRM instruments, even if similar behaviours should be observed. It is therefore recommended that each group characterizes its own instrument following the recommendations given in this study. Finally, the assessment of the limit of detection and total uncertainties is discussed and an example of field deployment of this CRM instrument is presented.

  15. Mechanical restraint in psychiatry

    DEFF Research Database (Denmark)

    Bak, Jesper; Zoffmann, Vibeke; Sestoft, Dorte Maria

    2014-01-01

    PURPOSE: To examine how potential mechanical restraint preventive factors in hospitals are associated with the frequency of mechanical restraint episodes. DESIGN AND METHODS: This study employed a retrospective association design, and linear regression was used to assess the associations. FINDINGS......: Three mechanical restraint preventive factors were significantly associated with low rates of mechanical restraint use: mandatory review (exp[B] = .36, p mechanical...

  16. Mechanical Behaviour of Materials Volume II Fracture Mechanics and Damage

    CERN Document Server

    François, Dominique; Zaoui, André

    2013-01-01

    Designing new structural materials, extending lifetimes and guarding against fracture in service are among the preoccupations of engineers, and to deal with these they need to have command of the mechanics of material behaviour. This ought to reflect in the training of students. In this respect, the first volume of this work deals with elastic, elastoplastic, elastoviscoplastic and viscoelastic behaviours; this second volume continues with fracture mechanics and damage, and with contact mechanics, friction and wear. As in Volume I, the treatment links the active mechanisms on the microscopic scale and the laws of macroscopic behaviour. Chapter I is an introduction to the various damage phenomena. Chapter II gives the essential of fracture mechanics. Chapter III is devoted to brittle fracture, chapter IV to ductile fracture and chapter V to the brittle-ductile transition. Chapter VI is a survey of fatigue damage. Chapter VII is devoted to hydogen embrittlement and to environment assisted cracking, chapter VIII...

  17. Applications of quantum mechanical techniques to areas outside of quantum mechanics

    CERN Document Server

    Khrennikov, Andrei

    2018-01-01

    This book deals with applications of quantum mechanical techniques to areas outside of quantum mechanics, so-called quantum-like modeling. Research in this area has grown over the last 15 years. But even already more than 50 years ago, the interaction between Physics Nobelist Pauli and the psychologist Carl Jung in the 1950's on seeking to find analogous uses of the complementarity principle from quantum mechanics in psychology needs noting. This book does NOT want to advance that society is quantum mechanical! The macroscopic world is manifestly not quantum mechanical. But this rules not out that one can use concepts and the mathematical apparatus from quantum physics in a macroscopic environment. A mainstay ingredient of quantum mechanics, is 'quantum probability' and this tool has been proven to be useful in the mathematical modelling of decision making. In the most basic experiment of quantum physics, the double slit experiment, it is known (from the works of A. Khrennikov) that the law of total probabi...

  18. Engineering mechanics

    CERN Document Server

    Gross, Dietmar; Schröder, Jörg; Wall, Wolfgang A; Rajapakse, Nimal

    Statics is the first volume of a three-volume textbook on Engineering Mechanics. The authors, using a time-honoured straightforward and flexible approach, present the basic concepts and principles of mechanics in the clearest and simplest form possible to advanced undergraduate engineering students of various disciplines and different educational backgrounds. An important objective of this book is to develop problem solving skills in a systematic manner. Another aim of this volume is to provide engineering students as well as practising engineers with a solid foundation to help them bridge the gap between undergraduate studies on the one hand and advanced courses on mechanics and/or practical engineering problems on the other. The book contains numerous examples, along with their complete solutions. Emphasis is placed upon student participation in problem solving. The contents of the book correspond to the topics normally covered in courses on basic engineering mechanics at universities and colleges. Now in i...

  19. Parametric study of control mechanism of cortical bone remodeling under mechanical stimulus

    Science.gov (United States)

    Wang, Yanan; Qin, Qing-Hua

    2010-03-01

    The control mechanism of mechanical bone remodeling at cellular level was investigated by means of an extensive parametric study on a theoretical model described in this paper. From a perspective of control mechanism, it was found that there are several control mechanisms working simultaneously in bone remodeling which is a complex process. Typically, an extensive parametric study was carried out for investigating model parameter space related to cell differentiation and apoptosis which can describe the fundamental cell lineage behaviors. After analyzing all the combinations of 728 permutations in six model parameters, we have identified a small number of parameter combinations that can lead to physiologically realistic responses which are similar to theoretically idealized physiological responses. The results presented in the work enhanced our understanding on mechanical bone remodeling and the identified control mechanisms can help researchers to develop combined pharmacological-mechanical therapies to treat bone loss diseases such as osteoporosis.

  20. Nonlinear mechanics a supplement to theoretical mechanics of particles and continua

    CERN Document Server

    Fetter, Alexander L

    2006-01-01

    In their prior Dover book, Theoretical Mechanics of Particles and Continua, Alexander L. Fetter and John Dirk Walecka provided a lucid and self-contained account of classical mechanics, together with appropriate mathematical methods. This supplement-an update of that volume-offers a bridge to contemporary mechanics.The original book's focus on continuum mechanics-with chapters on sound waves in fluids, surface waves on fluids, heat conduction, and viscous fluids-forms the basis for this supplement's discussion of nonlinear continuous systems. Topics include linearized stability analysis; a det

  1. Mechanical rebar splicing

    Directory of Open Access Journals (Sweden)

    Milosavljević Branko

    2014-01-01

    Full Text Available Different mechanical rebar splicing systems are presented, and design situations where mechanical splicing has advantage over reinforcement splicing by overlapping and welding are defined in this paper. New international standards for testing and proof of systems for mechanical rebar splicing quality are considered. Mechanical splicing system for rebar and bolt connection, usable in steel and reinforced concrete structural elements connections, is presented in this paper. There are only few examples of mechanical rebar splicing in our country. The most significant one - the pylon and beam connection at Ada Bridge in Belgrade is presented in the paper. Intensive development of production and use of mechanical rebar splicing systems, research in this area, as well as the publication of international standards prescribing requirements for quality and procedures for proof of quality, represent very good base for development of the corresponding technical norms in Serbia. The legislation in this area would quicken proof of quality procedures, attest and approval issuing for individual products, leading to wider use of this system in all situations where it is in advantage over the classical reinforcement splicing.

  2. Fluid mechanics as a driver of tissue-scale mechanical signaling in organogenesis.

    Science.gov (United States)

    Gilbert, Rachel M; Morgan, Joshua T; Marcin, Elizabeth S; Gleghorn, Jason P

    2016-12-01

    Organogenesis is the process during development by which cells self-assemble into complex, multi-scale tissues. Whereas significant focus and research effort has demonstrated the importance of solid mechanics in organogenesis, less attention has been given to the fluid forces that provide mechanical cues over tissue length scales. Fluid motion and pressure is capable of creating spatial gradients of forces acting on cells, thus eliciting distinct and localized signaling patterns essential for proper organ formation. Understanding the multi-scale nature of the mechanics is critically important to decipher how mechanical signals sculpt developing organs. This review outlines various mechanisms by which tissues generate, regulate, and sense fluid forces and highlights the impact of these forces and mechanisms in case studies of normal and pathological development.

  3. Defining Game Mechanics

    DEFF Research Database (Denmark)

    Sicart (Vila), Miguel Angel

    2008-01-01

    This article defins game mechanics in relation to rules and challenges. Game mechanics are methods invoked by agents for interacting with the game world. I apply this definition to a comparative analysis of the games Rez, Every Extend Extra and Shadow of the Colossus that will show the relevance...... of a formal definition of game mechanics. Udgivelsesdato: Dec 2008...

  4. A quantum mechanics/molecular mechanics study on the hydrolysis mechanism of New Delhi metallo-β-lactamase-1.

    Science.gov (United States)

    Zhu, Kongkai; Lu, Junyan; Liang, Zhongjie; Kong, Xiangqian; Ye, Fei; Jin, Lu; Geng, Heji; Chen, Yong; Zheng, Mingyue; Jiang, Hualiang; Li, Jun-Qian; Luo, Cheng

    2013-03-01

    New Delhi metallo-β-lactamase-1 (NDM-1) has emerged as a major global threat to human health for its rapid rate of dissemination and ability to make pathogenic microbes resistant to almost all known β-lactam antibiotics. In addition, effective NDM-1 inhibitors have not been identified to date. In spite of the plethora of structural and kinetic data available, the accurate molecular characteristics of and details on the enzymatic reaction of NDM-1 hydrolyzing β-lactam antibiotics remain incompletely understood. In this study, a combined computational approach including molecular docking, molecular dynamics simulations and quantum mechanics/molecular mechanics calculations was performed to characterize the catalytic mechanism of meropenem catalyzed by NDM-1. The quantum mechanics/molecular mechanics results indicate that the ionized D124 is beneficial to the cleavage of the C-N bond within the β-lactam ring. Meanwhile, it is energetically favorable to form an intermediate if no water molecule coordinates to Zn2. Moreover, according to the molecular dynamics results, the conserved residue K211 plays a pivotal role in substrate binding and catalysis, which is quite consistent with previous mutagenesis data. Our study provides detailed insights into the catalytic mechanism of NDM-1 hydrolyzing meropenem β-lactam antibiotics and offers clues for the discovery of new antibiotics against NDM-1 positive strains in clinical studies.

  5. Macro-mechanics controls quantum mechanics: mechanically controllable quantum conductance switching of an electrochemically fabricated atomic-scale point contact.

    Science.gov (United States)

    Staiger, Torben; Wertz, Florian; Xie, Fangqing; Heinze, Marcel; Schmieder, Philipp; Lutzweiler, Christian; Schimmel, Thomas

    2018-01-12

    Here, we present a silver atomic-scale device fabricated and operated by a combined technique of electrochemical control (EC) and mechanically controllable break junction (MCBJ). With this EC-MCBJ technique, we can perform mechanically controllable bistable quantum conductance switching of a silver quantum point contact (QPC) in an electrochemical environment at room temperature. Furthermore, the silver QPC of the device can be controlled both mechanically and electrochemically, and the operating mode can be changed from 'electrochemical' to 'mechanical', which expands the operating mode for controlling QPCs. These experimental results offer the perspective that a silver QPC may be used as a contact for a nanoelectromechanical relay.

  6. Mechanisms, Transmissions and Applications

    CERN Document Server

    Corves, Burkhard

    2012-01-01

    The first Workshop on Mechanisms, Transmissions and Applications -- MeTrApp-2011 was organized by the Mechatronics Department at the Mechanical Engineering Faculty, “Politehnica” University of Timisoara, Romania, under the patronage of the IFToMM Technical Committees Linkages and Mechanical Controls and Micromachines. The workshop brought together researchers and students who work in disciplines associated with mechanisms science and offered a great opportunity for scientists from all over the world to present their achievements, exchange innovative ideas and create solid international links, setting the trend for future developments in this important and creative field. The topics treated in this volume are mechanisms and machine design, mechanical transmissions, mechatronic and biomechanic applications, computational and experimental methods, history of mechanism and machine science and teaching methods.

  7. Indexing mechanisms

    International Nuclear Information System (INIS)

    Wood, A.G.; Parker, G.E.; Berry, R.

    1976-01-01

    It is stated that the indexing mechanism described can be used in a nuclear reactor fuel element inspection rig. It comprises a tubular body adapted to house a canister containing a number of fuel elements located longtitudinally, and has two chucks spaced apart for displacing the fuel elements longitudinally in a stepwise manner, together with a plunger mechanism for displacing them successively into the chucks. A measuring unit is located between the chucks for measuring the diameter of the fuel elements at intervals about their circumferences, and a secondary indexing mechanism is provided for rotating the measuring unit in a stepwise manner. (U.K.)

  8. Real-time observations of mechanical stimulus-induced enhancements of mechanical properties in osteoblast cells

    International Nuclear Information System (INIS)

    Zhang Xu; Liu Xiaoli; Sun Jialun; He Shuojie; Lee, Imshik; Pak, Hyuk Kyu

    2008-01-01

    Osteoblast, playing a key role in the pathophysiology of osteoporosis, is one of the mechanical stress sensitive cells. The effects of mechanical load-induced changes of mechanical properties in osteoblast cells were studied at real-time. Osteoblasts obtained from young Wister rats were exposed to mechanical loads in different frequencies and resting intervals generated by atomic force microscopy (AFM) probe tip and simultaneously measured the changes of the mechanical properties by AFM. The enhancement of the mechanical properties was observed and quantified by the increment of the apparent Young's modulus, E * . The observed mechanical property depended on the frequency of applied tapping loads. For the resting interval is 50 s, the mechanical load-induced enhancement of E * -values disappears. It seems that the enhanced mechanical property was recover able under no additional mechanical stimulus

  9. Mechanics rules cell biology

    Directory of Open Access Journals (Sweden)

    Wang James HC

    2010-07-01

    Full Text Available Abstract Cells in the musculoskeletal system are subjected to various mechanical forces in vivo. Years of research have shown that these mechanical forces, including tension and compression, greatly influence various cellular functions such as gene expression, cell proliferation and differentiation, and secretion of matrix proteins. Cells also use mechanotransduction mechanisms to convert mechanical signals into a cascade of cellular and molecular events. This mini-review provides an overview of cell mechanobiology to highlight the notion that mechanics, mainly in the form of mechanical forces, dictates cell behaviors in terms of both cellular mechanobiological responses and mechanotransduction.

  10. Molecular Electrical Doping of Organic Semiconductors: Fundamental Mechanisms and Emerging Dopant Design Rules.

    Science.gov (United States)

    Salzmann, Ingo; Heimel, Georg; Oehzelt, Martin; Winkler, Stefanie; Koch, Norbert

    2016-03-15

    Today's information society depends on our ability to controllably dope inorganic semiconductors, such as silicon, thereby tuning their electrical properties to application-specific demands. For optoelectronic devices, organic semiconductors, that is, conjugated polymers and molecules, have emerged as superior alternative owing to the ease of tuning their optical gap through chemical variability and their potential for low-cost, large-area processing on flexible substrates. There, the potential of molecular electrical doping for improving the performance of, for example, organic light-emitting devices or organic solar cells has only recently been established. The doping efficiency, however, remains conspicuously low, highlighting the fact that the underlying mechanisms of molecular doping in organic semiconductors are only little understood compared with their inorganic counterparts. Here, we review the broad range of phenomena observed upon molecularly doping organic semiconductors and identify two distinctly different scenarios: the pairwise formation of both organic semiconductor and dopant ions on one hand and the emergence of ground state charge transfer complexes between organic semiconductor and dopant through supramolecular hybridization of their respective frontier molecular orbitals on the other hand. Evidence for the occurrence of these two scenarios is subsequently discussed on the basis of the characteristic and strikingly different signatures of the individual species involved in the respective doping processes in a variety of spectroscopic techniques. The critical importance of a statistical view of doping, rather than a bimolecular picture, is then highlighted by employing numerical simulations, which reveal one of the main differences between inorganic and organic semiconductors to be their respective density of electronic states and the doping induced changes thereof. Engineering the density of states of doped organic semiconductors, the Fermi

  11. Relativistic quantum mechanics

    International Nuclear Information System (INIS)

    Ollitrault, J.Y.

    1998-12-01

    These notes form an introduction to relativistic quantum mechanics. The mathematical formalism has been reduced to the minimum in order to enable the reader to calculate elementary physical processes. The second quantification and the field theory are the logical followings of this course. The reader is expected to know analytical mechanics (Lagrangian and Hamiltonian), non-relativistic quantum mechanics and some basis of restricted relativity. The purpose of the first 3 chapters is to define the quantum mechanics framework for already known notions about rotation transformations, wave propagation and restricted theory of relativity. The next 3 chapters are devoted to the application of relativistic quantum mechanics to a particle with 0,1/5 and 1 spin value. The last chapter deals with the processes involving several particles, these processes require field theory framework to be thoroughly described. (A.C.)

  12. Engineering quantum mechanics

    CERN Document Server

    Ahn, Doyeol

    2011-01-01

    A clear introduction to quantum mechanics concepts Quantum mechanics has become an essential tool for modern engineering, particularly due to the recent developments in quantum computing as well as the rapid progress in optoelectronic devices. Engineering Quantum Mechanics explains the fundamentals of this exciting field, providing broad coverage of both traditional areas such as semiconductor and laser physics as well as relatively new yet fast-growing areas such as quantum computation and quantum information technology. The book begins with basic quantum mechanics, reviewing measurements and probability, Dirac formulation, the uncertainty principle, harmonic oscillator, angular momentum eigenstates, and perturbation theory. Then, quantum statistical mechanics is explored, from second quantization and density operators to coherent and squeezed states, coherent interactions between atoms and fields, and the Jaynes-Cummings model. From there, the book moves into elementary and modern applications, discussing s...

  13. Introduction to analytical mechanics

    CERN Document Server

    Gamalath, KAILW

    2011-01-01

    INTRODUCTION TO ANALYTICAL MECHANICS is an attempt to introduce the modern treatment of classical mechanics so that transition to many fields in physics can be made with the least difficulty. This book deal with the formulation of Newtonian mechanics, Lagrangian dynamics, conservation laws relating to symmetries, Hamiltonian dynamics Hamilton's principle, Poisson brackets, canonical transformations which are invaluable in formulating the quantum mechanics and Hamilton-Jacobi equation which provides the transition to wave mechanics.

  14. Defense Mechanisms: A Bibliography.

    Science.gov (United States)

    Pedrini, D. T.; Pedrini, Bonnie C.

    This bibliography includes studies of defense mechanisms, in general, and studies of multiple mechanisms. Defense mechanisms, briefly and simply defined, are the unconscious ego defendants against unpleasure, threat, or anxiety. Sigmund Freud deserves the clinical credit for studying many mechanisms and introducing them in professional literature.…

  15. Quantum mechanics as a natural generalization of classical statistical mechanics

    International Nuclear Information System (INIS)

    Xu Laizi; Qian Shangwu

    1994-01-01

    By comparison between equations of motion of geometrical optics (GO) and that of classical statistical mechanics (CSM), it is found that there should be an analogy between GO and CSM instead of GO and classical mechanics (CM). Furthermore, by comparison between the classical limit (CL) of quantum mechanics (QM) and CSM, the authors find that CL of QM is CSM not CM, hence they demonstrated that QM is a natural generalization of CSM instead of CM

  16. Study on a mechanical snubber with an adjustment mechanism for resisting force

    International Nuclear Information System (INIS)

    Ohmata, Kenichiro; Miyanaga, Hiroyuki.

    1991-01-01

    The mechanical snubber is an earthquakeproof device for a piping system under particular circumstances such as high temperature and radioactivity. It restrains the piping system by a strong resisting force during an earthquake. This strong force can cause elastic failure of grooves on a brake disk, where steel balls are placed. In this report, an improved mechanical snubber having an adjustment mechanism for resisting force is proposed in order to obtain a mechanical snubber which has almost the same restraint effect and less resisting force in comparison with a conventional mechanical snubber. The resisting force characteristics and the restraint effect of the improved mechanical snubber applied to a simple beam are discussed both numerically and experimentally. The digital simulations are carried out using the Continuous System Simulation Language (CSSL). (author)

  17. Current Solid Mechanics Research

    DEFF Research Database (Denmark)

    Tvergaard, Viggo

    2016-01-01

    About thirty years ago James Lighthill wrote an essay on “What is Mechanics?” With that he also included some examples of the applications of mechanics. While his emphasis was on fluid mechanics, his own research area, he also included examples from research activities in solid mechanics....

  18. Numerical Solutions of Mechanical Turbulent Filtration Equation Used in Mechatronics and Micro Mechanic

    OpenAIRE

    Hassan Fathabadi

    2013-01-01

    In this study, several novel numerical solutions are presented to solve the turbulent filtration equation and its special case called “Non-Newtonian mechanical filtration equation”. The turbulent filtration equation in porous media is a very important equation which has many applications to solve the problems appearing especially in mechatronics, micro mechanic and fluid mechanic. Many applied mechanical problems can be solved using this equation. For example, non-Newtonian mechanical filtrat...

  19. The Purdue Mechanics Freeform Classroom: A New Approach to Engineering Mechanics Education

    OpenAIRE

    Rhoads, Jeffrey F.; Nauman, Eric; Holloway, Beth M; Krousgrill, Charles Morton

    2014-01-01

    The [REMOVED] Mechanics Freeform Classroom: A New Approach to Engineering Mechanics EducationMotivated by the need to address the broad spectrum of learning styles embraced by today’sengineering students, a desire to encourage active, peer-to-peer, and self-learning, and a goal ofinteracting with every student despite ever-expanding enrollments, the mechanics faculty at[REMOVED] University have developed the [REMOVED] Mechanics Freeform Classroom(PMFC) -- a new approach to engineering mechani...

  20. Quantum mechanics

    CERN Document Server

    Fitzpatrick, Richard

    2015-01-01

    Quantum mechanics was developed during the first few decades of the twentieth century via a series of inspired guesses made by various physicists, including Planck, Einstein, Bohr, Schroedinger, Heisenberg, Pauli, and Dirac. All these scientists were trying to construct a self-consistent theory of microscopic dynamics that was compatible with experimental observations. The purpose of this book is to present quantum mechanics in a clear, concise, and systematic fashion, starting from the fundamental postulates, and developing the theory in as logical manner as possible. Topics covered in the book include the fundamental postulates of quantum mechanics, angular momentum, time-dependent and time-dependent perturbation theory, scattering theory, identical particles, and relativistic electron theory.

  1. Mechanics

    CERN Document Server

    Hartog, J P Den

    1961-01-01

    First published over 40 years ago, this work has achieved the status of a classic among introductory texts on mechanics. Den Hartog is known for his lively, discursive and often witty presentations of all the fundamental material of both statics and dynamics (and considerable more advanced material) in new, original ways that provide students with insights into mechanical relationships that other books do not always succeed in conveying. On the other hand, the work is so replete with engineering applications and actual design problems that it is as valuable as a reference to the practicing e

  2. Insights into the catalytic mechanism of dehydrogenase BphB: A quantum mechanics/molecular mechanics study.

    Science.gov (United States)

    Zhang, Ruiming; Shi, Xiangli; Sun, Yanhui; Zhang, Qingzhu; Wang, Wenxing

    2018-05-17

    The present study delineated the dehydrogenation mechanism of cis-2,3-dihydro-2,3-dihydroxybiphenyl (2,3-DDBPH) and cis-2,3-dihydro-2,3-dihydroxy-4,4'-dichlorobiphenyl (2,3-DD-4,4'-DBPH) by Pandoraea pnomenusa strain B-356 cis-2,3-dihydro-2,3-dihydroxybiphenyl dehydrogenase (BphB) in atomistic detail. The enzymatic process was investigated by a combined quantum mechanics/molecular mechanics (QM/MM) approach. Five different snapshots were extracted and calculated, which revealed that the Boltzmann-weighted average barriers of 2,3-DDBPH and 2,3-DD-4,4'-DBPH dehydrogenation processes are 10.7 and 11.5 kcal mol -1 , respectively. The established dehydrogenation mechanism provides new insight into the degradation processes of other chlorinated 2,3-DDBPH. In addition to Asn115, Ser142, and Lys149, the importance of Ile 89, Asn143, Pro184, Met 187, Thr189, and Lue 191 during the dehydrogenation process of 2,3-DDBPH and 2,3-DD-4,4'-DBPH were also highlighted to search for promising mutation targets for improving the catalytic efficiency of BphB. Copyright © 2018. Published by Elsevier Ltd.

  3. Structural and Chemical Properties of the Nitrogen-Rich Energetic Material Triaminoguanidinium 1-methyl-5-nitriminotetrazolate under Pressure

    Science.gov (United States)

    2012-08-01

    ABSTRACT 16. SECURITY CLASSIFICATION OF: The structural and chemical properties of the bi-molecular, hydrogen-bonded, nitrogen-rich ener- getic...School Apprenticeship Program (ARO-HSAP), and the Depart- ment of Energy National Nuclear Security Administration (Carnegie/DOE Alliance Center; DE-FC52...B. J. Baer, H. Cynn, W. J. Evans, V. Iota , and C. S. Yoo, Phys. Rev. B 76(1), 014113 (2007). 9T. M. Klapötke, J. Stierstorfer, and A. U. Wallek, Chem

  4. Quantum mode phonon forces between chainmolecules

    DEFF Research Database (Denmark)

    Bohr, Jakob

    2001-01-01

    bimolecular interaction is a truly many-body force that is temperature dependent and can be of the order of 1 eV. These phonon forces depend on molecular shape, composition, and density. They may therefore also be important for large molecular conformational changes, including the unfolding of chain molecules....... For the later case, a significant change in zero-point energy is found. This may be the underlying cause for cold denaturation of proteins. (C) 2001 John Wiley & Sons, Inc....

  5. On the influence of alkali metal- and alkaline earth metal chlorides on the rate on inhibition of cholinesterases by organic phosphorus inhibitors

    International Nuclear Information System (INIS)

    Brestkin, A.P.; Shataeva, G.A.

    1975-01-01

    Influence of LiCl, NaCl, KCl, RbCl, CsCl, MgCl 2 , CaCl 2 , CrCl 2 , BaCl 2 on bimolecular constant (K 2 ) of the interaction rate of acetylcholinesterazo (ACE) and butylcholinesterazo (BuCE) with phosphororganic inhibitors was studied. K 2 value with increasing of the electrolite concentration for the interaction of ACE and BuCE with charged inhibitor is significantly decreased and significantly increased in case of interaction with neutral inhibitor

  6. Abrasive wear mechanisms and surface layer structure of refractory materials after mechanical working

    International Nuclear Information System (INIS)

    Milman, Y.V.; Lotsko, D.V.

    1989-01-01

    The mechanisms of abrasive wear and surface layer structure formation after different kinds of mechanical working are considered in terms of fracture and plastic deformation mechanisms for various refractory materials. The principles for classification of abrasive wear mechanisms are proposed, the four types of wear mechanisms are distinguished for various combinations of fractures and plastic deformation types. The concept of characteristic deformation temperature t * (knee temperature) is used. Detailed examples are given of investigating the surface layer structures in grinded crystals of sapphire and molybdenum. The amorphisation tendency of the thinnest surface layer while mechanical polishing is discussed separately. 19 refs., 11 figs., 2 tabs. (Author)

  7. A Novel Method of Mechanical Oxidation of CNT for Polymer Nanocomposite Application: Evaluation of Mechanical, Dynamic Mechanical, and Rheological Properties

    Directory of Open Access Journals (Sweden)

    Priyanka Pandey

    2014-01-01

    Full Text Available A new approach of oxidation of carbon nanotubes has been used to oxidize the CNTs. A comparative aspect of the mechanical oxidation and acid oxidation process has been established. FTIR analysis and titration method have shown the higher feasibility of the mechanical oxidation method to oxidize the CNTs. Comparatively less damage to the CNTs has been observed in case of mechanically oxidized as compared to acid oxidized CNTs. The mechanical properties of the nanocomposites reinforced with the acid oxidized CNT (ACNT and mechanically oxidized CNTs (McCNT were analyzed and relatively higher properties in the nanocomposites reinforced with McCNT were noticed. The less degree of entanglement in the McCNTs was noticed as compared to ACNTs. The dynamic mechanical analysis of the nanocomposites revealed much improved load transfer capability in the McCNT reinforced composites. Further, the rheological properties of the nanocomposites revealed the higher performance of McCNT reinforced composites.

  8. Mechanical Systems, Classical Models

    CERN Document Server

    Teodorescu, Petre P

    2009-01-01

    This third volume completes the Work Mechanical Systems, Classical Models. The first two volumes dealt with particle dynamics and with discrete and continuous mechanical systems. The present volume studies analytical mechanics. Topics like Lagrangian and Hamiltonian mechanics, the Hamilton-Jacobi method, and a study of systems with separate variables are thoroughly discussed. Also included are variational principles and canonical transformations, integral invariants and exterior differential calculus, and particular attention is given to non-holonomic mechanical systems. The author explains in detail all important aspects of the science of mechanics, regarded as a natural science, and shows how they are useful in understanding important natural phenomena and solving problems of interest in applied and engineering sciences. Professor Teodorescu has spent more than fifty years as a Professor of Mechanics at the University of Bucharest and this book relies on the extensive literature on the subject as well as th...

  9. Mechanics and uncertainty

    CERN Document Server

    Lemaire, Maurice

    2014-01-01

    Science is a quest for certainty, but lack of certainty is the driving force behind all of its endeavors. This book, specifically, examines the uncertainty of technological and industrial science. Uncertainty and Mechanics studies the concepts of mechanical design in an uncertain setting and explains engineering techniques for inventing cost-effective products. Though it references practical applications, this is a book about ideas and potential advances in mechanical science.

  10. Complications of mechanical ventilation

    Directory of Open Access Journals (Sweden)

    Drašković Biljana

    2011-01-01

    Full Text Available Mechanical ventilation of the lungs, as an important therapeutic measure, cannot be avoided in critically ill patients. However, when machines take over some of vital functions there is always a risk of complications and accidents. Complications associated with mechanical ventilation can be divided into: 1 airway-associated complications; 2 complications in the response of patients to mechanical ventilation; and 3 complications related to the patient’s response to the device for mechanical ventilation. Complications of artificial airway may be related to intubation and extubation or the endotracheal tube. Complications of mechanical ventilation, which arise because of the patient’s response to mechanical ventilation, may primarily cause significant side effects to the lungs. During the last two decades it was concluded that mechanical ventilation can worsen or cause acute lung injury. Mechanical ventilation may increase the alveolar/capillary permeability by overdistension of the lungs (volutrauma, it can exacerbate lung damage due to the recruitment/derecruitment of collapsed alveoli (atelectrauma and may cause subtle damages due to the activation of inflammatory processes (biotrauma. Complications caused by mechanical ventilation, beside those involving the lungs, can also have significant effects on other organs and organic systems, and can be a significant factor contributing to the increase of morbidity and mortality in critically ill of mechanically ventilated patients. Complications are fortunately rare and do not occur in every patient, but due to their seriousness and severity they require extensive knowledge, experience and responsibility by health-care workers.

  11. CH3CO + O2 + M (M = He, N2) Reaction Rate Coefficient Measurements and Implications for the OH Radical Product Yield.

    Science.gov (United States)

    Papadimitriou, Vassileios C; Karafas, Emmanuel S; Gierczak, Tomasz; Burkholder, James B

    2015-07-16

    The gas-phase CH3CO + O2 reaction is known to proceed via a chemical activation mechanism leading to the formation of OH and CH3C(O)OO radicals via bimolecular and termolecular reactive channels, respectively. In this work, rate coefficients, k, for the CH3CO + O2 reaction were measured over a range of temperature (241-373 K) and pressure (0.009-600 Torr) with He and N2 as the bath gas and used to characterize the bi- and ter-molecular reaction channels. Three independent experimental methods (pulsed laser photolysis-laser-induced fluorescence (PLP-LIF), pulsed laser photolysis-cavity ring-down spectroscopy (PLP-CRDS), and a very low-pressure reactor (VLPR)) were used to characterize k(T,M). PLP-LIF was the primary method used to measure k(T,M) in the high-pressure regime under pseudo-first-order conditions. CH3CO was produced by PLP, and LIF was used to monitor the OH radical bimolecular channel reaction product. CRDS, a complementary high-pressure method, measured k(295 K,M) over the pressure range 25-600 Torr (He) by monitoring the temporal CH3CO radical absorption following its production via PLP in the presence of excess O2. The VLPR technique was used in a relative rate mode to measure k(296 K,M) in the low-pressure regime (9-32 mTorr) with CH3CO + Cl2 used as the reference reaction. A kinetic mechanism analysis of the combined kinetic data set yielded a zero pressure limit rate coefficient, kint(T), of (6.4 ± 4) × 10(-14) exp((820 ± 150)/T) cm(3) molecule(-1) s(-1) (with kint(296 K) measured to be (9.94 ± 1.3) × 10(-13) cm(3) molecule(-1) s(-1)), k0(T) = (7.39 ± 0.3) × 10(-30) (T/300)(-2.2±0.3) cm(6) molecule(-2) s(-1), and k∞(T) = (4.88 ± 0.05) × 10(-12) (T/300)(-0.85±0.07) cm(3) molecule(-1) s(-1) with Fc = 0.8 and M = N2. A He/N2 collision efficiency ratio of 0.60 ± 0.05 was determined. The phenomenological kinetic results were used to define the pressure and temperature dependence of the OH radical yield in the CH3CO + O2 reaction. The

  12. Mechanical design in embryos: mechanical signalling, robustness and developmental defects.

    Science.gov (United States)

    Davidson, Lance A

    2017-05-19

    Embryos are shaped by the precise application of force against the resistant structures of multicellular tissues. Forces may be generated, guided and resisted by cells, extracellular matrix, interstitial fluids, and how they are organized and bound within the tissue's architecture. In this review, we summarize our current thoughts on the multiple roles of mechanics in direct shaping, mechanical signalling and robustness of development. Genetic programmes of development interact with environmental cues to direct the composition of the early embryo and endow cells with active force production. Biophysical advances now provide experimental tools to measure mechanical resistance and collective forces during morphogenesis and are allowing integration of this field with studies of signalling and patterning during development. We focus this review on concepts that highlight this integration, and how the unique contributions of mechanical cues and gradients might be tested side by side with conventional signalling systems. We conclude with speculation on the integration of large-scale programmes of development, and how mechanical responses may ensure robust development and serve as constraints on programmes of tissue self-assembly.This article is part of the themed issue 'Systems morphodynamics: understanding the development of tissue hardware'. © 2017 The Author(s).

  13. Mechanical Design of Downhole Tractor Based on Two-Way Self-locking Mechanism

    Science.gov (United States)

    Fang, Delei; Shang, Jianzhong; Luo, Zirong; Wu, Guoheng; Liu, Yiying

    2018-03-01

    Based on the technology of horizontal well tractor, a kind of downhole tractor was developed which can realize Two-Way self-locking function. Aiming at the needs of horizontal well logging to realize the target of small size, high traction and high reliability, the tractor selects unique heart-shaped CAM as the locking mechanism. The motion principle of telescopic downhole tractor, the design of mechanical structure and locking principle of the locking mechanism are all analyzed. The mathematical expressions of traction are obtained by mechanical analysis of parallel support rod in the locking mechanism. The force analysis and contour design of the heart-shaped CAM are performed, which can lay the foundation for the development of tractor prototype.

  14. Technical report on micro-mechanical versus conventional modelling in non-linear fracture mechanics

    International Nuclear Information System (INIS)

    2001-07-01

    While conventional fracture mechanics is capable of predicting crack growth behaviour if sufficient experimental observations are available, micro-mechanical modelling can both increase the accuracy of these predictions and model phenomena that are inaccessible by the conventional theory such as the ductile-cleavage temperature transition. A common argument against micro-mechanical modelling is that it is too complicated for use in routine engineering applications. This is both a computational and an educational problem. That micro-mechanical modelling is unnecessarily complicated is certainly true in many situations. The on-going development of micro-mechanical models, computational algorithms and computer speed will however most probably diminish the computational problem rather rapidly. Compare for instance the rate of development of computational methods for structural analysis. Meanwhile micro-mechanical modelling may serve as a tool by which more simplified engineering methods can be validated. The process of receiving a wide acceptance of the new methods is probably much slower. This involves many steps. First the research community must be in reasonable agreement on the methods and their use. Then the methods have to be implemented into computer software and into code procedures. The development and acceptance of conventional fracture mechanics may serve as an historical example of the time required before a new methodology has received a wide usage. The CSNI Working Group on Integrity and Ageing (IAGE) decided to carry out a report on micro-mechanical modeling to promote this promising and valuable technique. The report presents a comparison with non-linear fracture mechanics and highlights key aspects that could lead to a better knowledge and accurate predictions. Content: - 1. Introduction; - 2. Concepts of non-linear fracture mechanics with point crack tip modelling; - 3. Micro-mechanical models for cleavage fracture; - 4, Micro-mechanical modelling of

  15. Mechanical deformation of atomic-scale metallic contacts: Structure and mechanisms

    DEFF Research Database (Denmark)

    Sørensen, Mads Reinholdt; Brandbyge, Mads; Jacobsen, Karsten Wedel

    1998-01-01

    We have simulated the mechanical deformation of atomic-scale metallic contacts under tensile strain using molecular dynamics and effective medium theory potentials. The evolution of the structure of the contacts and the underlying deformation mechanisms are described along with the calculated......, but vacancies can be permanently present. The transition states and energies for slip mechanisms have been determined using the nudged elastic band method, and we find a size-dependent crossover from a dislocation-mediated slip to a homogeneous slip when the contact diameter becomes less than a few nm. We show...

  16. Mechanical and electro-mechanical properties of three-dimensional nanoporous graphene-poly(vinylidene fluoride composites

    Directory of Open Access Journals (Sweden)

    G. P. Zheng

    2016-09-01

    Full Text Available Three-dimensional nanoporous graphene monoliths are utilized to prepare graphene-poly(vinylidene fluoride nanocomposites with enhanced mechanical and electro-mechanical properties. Pre-treatment of the polymer (poly(vinylidene fluoride, PVDF with graphene oxides (GOs facilitates the formation of uniform and thin PVDF films with a typical thickness below 100 nm well coated at the graphene nano-sheets. Besides their excellent compressibility, ductility and mechanical strength, the nanoporous graphene-PVDF nanocomposites are found to possess high sensitivity in strain-dependent electrical conductivity. The improved mechanical and electro-mechanical properties are ascribed to the enhanced crystalline β phase in PVDF which possesses piezoelectricity. The mechanical relaxation analyses on the interfaces between graphene and PVDF reveal that the improved mechanical and electro-mechanical properties could result from the interaction between the –C=O groups in the nanoporous graphene and the –CF2 groups in PVDF, which also explains the important role of GOs in the preparation of the graphene-polymer nanocomposites with superior combined mechanical and electro-mechanical properties.

  17. Generalized mechanics as a representation of the ordinary mechanics

    International Nuclear Information System (INIS)

    Knapecz, G.

    1974-01-01

    It is shown that the generalized mechanics of one masspoint may be interpreted as a special representation of the ordinary mechanics of a system of masspoints. The hormorphism of both representations is shown in the case of two masspoints coupled by a harmonic force. The new representation is applied in the special relativic meachanics of mass-points. (author)

  18. Quantum Mechanics/Molecular Mechanics Simulations Identify the Ring-Opening Mechanism of Creatininase.

    Science.gov (United States)

    Jitonnom, Jitrayut; Mujika, Jon I; van der Kamp, Marc W; Mulholland, Adrian J

    2017-12-05

    Creatininase catalyzes the conversion of creatinine (a biosensor for kidney function) to creatine via a two-step mechanism: water addition followed by ring opening. Water addition is common to other known cyclic amidohydrolases, but the precise mechanism for ring opening is still under debate. The proton donor in this step is either His178 or a water molecule bound to one of the metal ions, and the roles of His178 and Glu122 are unclear. Here, the two possible reaction pathways have been fully examined by means of combined quantum mechanics/molecular mechanics simulations at the SCC-DFTB/CHARMM22 level of theory. The results indicate that His178 is the main catalytic residue for the whole reaction and explain its role as proton shuttle during the ring-opening step. In the first step, His178 provides electrostatic stabilization to the gem-diolate tetrahedral intermediate. In the second step, His178 abstracts the hydroxyl proton of the intermediate and delivers it to the cyclic amide nitrogen, leading to ring opening. The latter is the rate-limiting step with a free energy barrier of 18.5 kcal/mol, in agreement with the experiment. We find that Glu122 must be protonated during the enzyme reaction, so that it can form a stable hydrogen bond with its neighboring water molecule. Simulations of the E122Q mutant showed that this replacement disrupts the H-bond network formed by three conserved residues (Glu34, Ser78, and Glu122) and water, increasing the energy barrier. Our computational studies provide a comprehensive explanation for previous structural and kinetic observations, including why the H178A mutation causes a complete loss of activity but the E122Q mutation does not.

  19. Compliant Space Mechanisms

    Data.gov (United States)

    National Aeronautics and Space Administration — OBJECTIVES The proposed research will combine the areas of compliant mechanisms and space technology. Compliant mechanisms perform their function through the elastic...

  20. Mechanism of laser micro-adjustment

    International Nuclear Information System (INIS)

    Shen Hong

    2008-01-01

    Miniaturization is a requirement in engineering to produce competitive products in the field of optical and electronic industries. Laser micro-adjustment is a new and promising technology for sheet metal actuator systems. Efforts have been made to understand the mechanisms of metal plate forming using a laser heating source. Three mechanisms have been proposed for describing the laser forming processes in different scenarios, namely the temperature gradient mechanism (TGM), buckling mechanism and upsetting mechanism (UM). However, none of these mechanisms can fully describe the deformation mechanisms involved in laser micro-adjustment. Based on the thermal and elastoplastic analyses, a coupled TGM and UM are presented in this paper to illustrate the thermal mechanical behaviours of two-bridge actuators when applying a laser forming process. To validate the proposed coupling mechanism, numerical simulations are carried out and the corresponding results demonstrate the mechanism proposed. The mechanism of the micro-laser adjustment could be taken as a supplement to the laser forming process.

  1. Supersymmetric mechanics. Vol. 2. The attractor mechanism and space time singularities

    International Nuclear Information System (INIS)

    Bellucci, S.; Marrani, A.; Ferrara, S.

    2006-01-01

    This is the second volume in a series of books on the general theme of Supersymmetric Mechanics; the series is based on lectures and discussions held in 2005 and 2006 at the INFN-Laboratori Nazionali di Frascati. The first volume appears as Lect. Notes Physics, Vol. 698 ''Supersymmetric Mechanics, Vol.1: Supersymmetry, Noncommutativity and Matrix Models'' (2006) ISBN: 3-540-33313-4. The present extensive lecture supplies a pedagogical introduction, at the non-expert level, to the attractor mechanism in space-time singularities. In such a framework, supersymmetry seems to be related to dynamical systems with fixed points, describing the equilibrium state and the stability features of the thermodynamics of black holes. After a qualitative overview, explicit examples realizing the attractor mechanism are treated at some length; they include relevant cases of asymptotically flat, maximal and non-maximal, extended supergravities in 4 and 5 dimensions. A number of recent advances along various directions of research on the attractor mechanism are also given. (orig.)

  2. Mechanistic investigations of novel photoinitiators for radical polymerization

    International Nuclear Information System (INIS)

    Griesser, M.

    2012-01-01

    Nowadays, there is a wide variety of photoinitiators (PIs) available for radical polymerizations. A common example are two-component (Type II) systems such as benzophenone and tertiary amines. However these systems also suffer from problems due to bimolecularity. These include the possible back electron transfer (BET) leading to deactivation, as well as the solvent cage effect, occurring in highly viscous media. The aim of this thesis was to investigate the reaction mechanism of several photoinitiating systems, which show superior performance. Moreover, they exhibit additional benefits such as circumvention of oxygen inhibition by decarboxylation. Thereby this work helps to understand the molecular basis of the performance of different PI systems. In vestigated PIs included benzaldoxime esters, covalently linked benzophenone and N-phenylglycine as well as derivatives of both systems. Furthermore a PI based on benzophenone extended by ethynyl moeities is discussed. The main tool in this investigation was photo-CIDNP (chemically induced dynamic nuclear polarization), an NMR based technique for studying radical reactions. A complementary view was obtained with TR-EPR (time-resolved electron paramagnetic resonance), which provides direct information about the active radical species. The results were further compared with quantum mechanical calculations (DFT) of the magnetic properties of the radicals. The theoretical approach was further applied to other paramagnetic species such as donor-acceptor systems. (author) [de

  3. Mechanistic Study of the Gas-Phase In-Source Hofmann Elimination of Doubly Quaternized Cinchona-Alkaloid Based Phase-Transfer Catalysts by (+)-Electrospray Ionization/Tandem Mass Spectrometry.

    Science.gov (United States)

    Yang, Rong-Sheng; Sheng, Huaming; Lexa, Katrina W; Sherer, Edward C; Zhang, Li-Kang; Xiang, Bangping; Helmy, Roy; Mao, Bing

    2017-03-01

    An unusual in-source fragmentation pattern observed for 14 doubly quaternized cinchona alkaloid-based phase-transfer catalysts (PTC) was studied using (+)-ESI high resolution mass spectrometry. Loss of the substituted benzyl cation (R1 or R2) was found to be the major product ion [M 2+ - R 1 + or R 2 + ] + in MS spectra of all PTC compounds. A Hofmann elimination product ion [M - H] + was also observed. Only a small amount of the doubly charged M 2+ ions were observed in the MS spectra, likely due to strong Columbic repulsion between the two quaternary ammonium cations in the gas phase. The positive voltage in the MS inlet but not the ESI probe was found to induce this extensive fragmentation for all PTC diboromo-salts. Compound 1 was used as an example to illustrate the proposed in-source fragmentation mechanism. The mechanism of formation of the Hofmann elimination product ion [M - H] + was further investigated using HRMS/MS, H/D exchange, and DFT calculations. The proposed formation of 2b as the major Hofmann elimination product ion was supported both by HRMS/MS and DFT calculations. Formation of product ion 2b through a concerted unimolecular E i elimination pathway is proposed rather than a bimolecular E2 elimination pathway for common solution Hofmann eliminations. Graphical Abstract ᅟ.

  4. Mechanical Testing of MLCCs

    Science.gov (United States)

    Teverovsky, Alexander A.

    2016-01-01

    Cracking of multilayer ceramic capacitors, MLCCs, remains a serious problem for space systems. This problem increases substantially for large size capacitors and in cases when manual soldering is involved or the system experiences mechanical shock or vibration. In any case, a fracture occurs when the sum of external and internal mechanical stresses exceeds the strength of the part. To reduce the probability of cracking, the level of stress should be reduced, e.g. by optimizing the assembly workmanship and rules for board design, and the strength of the parts increased by selecting the most mechanically robust capacitors. The latter might possibly be achieved by selecting MLCCs based on the in-situ measurements of mechanical characteristics using four types of tests: flexural strength, hardness, fracture toughness, and flex bend testing. Note that military specifications MIL-PRF-123 and MIL-PRF-55681 do not have requirements for mechanical testing of the parts. However, specifications for automotive industry components employ two types of mechanical tests: beam load (break strength) test per AEC-Q200-003 and board flex test per AEC-Q200-005. A recent military specification for thin dielectric capacitors, MIL-PRF-32535, has one mechanical test, board flex testing, that is similar to AEC-Q200-005. The purpose of this report was assessment of the efficiency of different mechanical tests for selection robust capacitors and comparison of mechanical characteristics of Base Metal Electrode (BME) and Precious Metal Electrode (PME) capacitors. The report has three parts related to the first three mechanical tests mentioned above.

  5. Equilibrium statistical mechanics

    CERN Document Server

    Jackson, E Atlee

    2000-01-01

    Ideal as an elementary introduction to equilibrium statistical mechanics, this volume covers both classical and quantum methodology for open and closed systems. Introductory chapters familiarize readers with probability and microscopic models of systems, while additional chapters describe the general derivation of the fundamental statistical mechanics relationships. The final chapter contains 16 sections, each dealing with a different application, ordered according to complexity, from classical through degenerate quantum statistical mechanics. Key features include an elementary introduction t

  6. The equivalence principle in classical mechanics and quantum mechanics

    OpenAIRE

    Mannheim, Philip D.

    1998-01-01

    We discuss our understanding of the equivalence principle in both classical mechanics and quantum mechanics. We show that not only does the equivalence principle hold for the trajectories of quantum particles in a background gravitational field, but also that it is only because of this that the equivalence principle is even to be expected to hold for classical particles at all.

  7. On obtaining classical mechanics from quantum mechanics

    International Nuclear Information System (INIS)

    Date, Ghanashyam

    2007-01-01

    Constructing a classical mechanical system associated with a given quantum-mechanical one entails construction of a classical phase space and a corresponding Hamiltonian function from the available quantum structures and a notion of coarser observations. The Hilbert space of any quantum-mechanical system naturally has the structure of an infinite-dimensional symplectic manifold ('quantum phase space'). There is also a systematic, quotienting procedure which imparts a bundle structure to the quantum phase space and extracts a classical phase space as the base space. This works straightforwardly when the Hilbert space carries weakly continuous representation of the Heisenberg group and one recovers the linear classical phase space R 2N . We report on how the procedure also allows extraction of nonlinear classical phase spaces and illustrate it for Hilbert spaces being finite dimensional (spin-j systems), infinite dimensional but separable (particle on a circle) and infinite dimensional but non-separable (polymer quantization). To construct a corresponding classical dynamics, one needs to choose a suitable section and identify an effective Hamiltonian. The effective dynamics mirrors the quantum dynamics provided the section satisfies conditions of semiclassicality and tangentiality

  8. Mechanical ventilator - infants

    Science.gov (United States)

    ... this page: //medlineplus.gov/ency/article/007240.htm Mechanical ventilator - infants To use the sharing features on this page, please enable JavaScript. A mechanical ventilator is a machine that assists with breathing. ...

  9. Supersymmetric classical mechanics

    International Nuclear Information System (INIS)

    Biswas, S.N.; Soni, S.K.

    1986-01-01

    The purpose of the paper is to construct a supersymmetric Lagrangian within the framework of classical mechanics which would be regarded as a candidate for passage to supersymmetric quantum mechanics. 5 refs. (author)

  10. Biological Applications of Hybrid Quantum Mechanics/Molecular Mechanics Calculation

    Directory of Open Access Journals (Sweden)

    Jiyoung Kang

    2012-01-01

    Full Text Available Since in most cases biological macromolecular systems including solvent water molecules are remarkably large, the computational costs of performing ab initio calculations for the entire structures are prohibitive. Accordingly, QM calculations that are jointed with MM calculations are crucial to evaluate the long-range electrostatic interactions, which significantly affect the electronic structures of biological macromolecules. A UNIX-shell-based interface program connecting the quantum mechanics (QMs and molecular mechanics (MMs calculation engines, GAMESS and AMBER, was developed in our lab. The system was applied to a metalloenzyme, azurin, and PU.1-DNA complex; thereby, the significance of the environmental effects on the electronic structures of the site of interest was elucidated. Subsequently, hybrid QM/MM molecular dynamics (MD simulation using the calculation system was employed for investigation of mechanisms of hydrolysis (editing reaction in leucyl-tRNA synthetase complexed with the misaminoacylated tRNALeu, and a novel mechanism of the enzymatic reaction was revealed. Thus, our interface program can play a critical role as a powerful tool for state-of-the-art sophisticated hybrid ab initio QM/MM MD simulations of large systems, such as biological macromolecules.

  11. Kinetics of Reactive Fronts in Porous Media: quantification through a laboratory experiment

    Science.gov (United States)

    De Anna, P.; Jimenez-Martinez, J.; Turuban, R.; Tabuteau, H.; Derrien, M.; Le Borgne, T.; Meheust, Y.

    2013-12-01

    The kinetics of reaction fronts in heterogeneous flows is tightly linked to the mixing dynamics governed by the combined action of stretching, diffusion and dispersion. Focusing on porous media flows, with a new experimental setup we show that the invading solute is organized into stretched lamellae, whose deformation and coalescence control the effective reaction kinetics of the mixing limited bimolecular reaction A + B --> C. While the classic advection-dispersion theory predicts a scaling of the cumulative product mass of C as t^(0.5), we observe two distinct kinetics regimes, one characterized by the stretching and the other by the coalescence of the invading lamellae, in which the mass of C scales faster than t^(0.5). The proposed experimental set up allows for direct quantification of mixing and reactive transport in porous media with a high spatial resolution, at the pore scale. The analogous two dimensional porous medium consists in a Hele-Shaw cell containing a single layer of cylindrical solid grains built by soft lithography. On the one hand, the measurement of the local, intra-pore, conservative concentration field is done using a fluorescent tracer. On the other hand, considering a fast bimolecular advection-dispersion reaction A + B --> C occurring as A displaces B, we quantify the reaction kinetics from the spatially-resolved measurement of the pore scale reaction rate, using a chemiluminescent reaction.

  12. THE ROLE OF NITROGEN IN TITAN’S UPPER ATMOSPHERIC HYDROCARBON CHEMISTRY OVER THE SOLAR CYCLE

    Energy Technology Data Exchange (ETDEWEB)

    Luspay-Kuti, A.; Mandt, K. E.; Greathouse, T. K. [Department of Space Research, Southwest Research Institute, San Antonio, TX 78228 (United States); Westlake, J. H. [Johns Hopkins University Applied Physics Laboratory, Laurel, MD 20723 (United States); Plessis, S., E-mail: aluspaykuti@swri.edu [Fund Kis, F-92160 Antony (France)

    2016-06-01

    Titan’s thermospheric photochemistry is primarily driven by solar radiation. Similarly to other planetary atmospheres, such as Mars’, Titan’s atmospheric structure is also directly affected by variations in the solar extreme-UV/UV output in response to the 11-year-long solar cycle. Here, we investigate the influence of nitrogen on the vertical production, loss, and abundance profiles of hydrocarbons as a function of the solar cycle. Our results show that changes in the atmospheric nitrogen atomic density (primarily in its ground state N({sup 4}S)) as a result of photon flux variations have important implications for the production of several minor hydrocarbons. The solar minimum enhancement of CH{sub 3}, C{sub 2}H{sub 6}, and C{sub 3}H{sub 8}, despite the lower CH{sub 4} photodissociation rates compared with solar maximum conditions, is explained by the role of N({sup 4}S). N({sup 4}S) indirectly controls the altitude of termolecular versus bimolecular chemical regimes through its relationship with CH{sub 3}. When in higher abundance during solar maximum at lower altitudes, N({sup 4}S) increases the importance of bimolecular CH{sub 3} + N({sup 4}S) reactions producing HCN and H{sub 2}CN. The subsequent remarkable CH{sub 3} loss and decrease in the CH{sub 3} abundance at lower altitudes during solar maximum affects the overall hydrocarbon chemistry.

  13. Equilibrium statistical mechanics

    CERN Document Server

    Mayer, J E

    1968-01-01

    The International Encyclopedia of Physical Chemistry and Chemical Physics, Volume 1: Equilibrium Statistical Mechanics covers the fundamental principles and the development of theoretical aspects of equilibrium statistical mechanics. Statistical mechanical is the study of the connection between the macroscopic behavior of bulk matter and the microscopic properties of its constituent atoms and molecules. This book contains eight chapters, and begins with a presentation of the master equation used for the calculation of the fundamental thermodynamic functions. The succeeding chapters highlight t

  14. Mechanical Material Engineering

    International Nuclear Information System (INIS)

    Kim, Mun Il

    1993-01-01

    This book introduced mechanical material with introduction, basic problems about metal ingredient of machine of metal and alloy, property of metal material mechanical metal material such as categorization of metal material and high tensile structure steel, mechanic design and steel material with three important points on using of steel materials, selection and directions machine structural steel, selection and directions of steel for tool, selection and instruction of special steel like stainless steel and spring steel, nonferrous metal materials and plastic.

  15. HYDRAULIC SERVO CONTROL MECHANISM

    Science.gov (United States)

    Hussey, R.B.; Gottsche, M.J. Jr.

    1963-09-17

    A hydraulic servo control mechanism of compact construction and low fluid requirements is described. The mechanism consists of a main hydraulic piston, comprising the drive output, which is connected mechanically for feedback purposes to a servo control piston. A control sleeve having control slots for the system encloses the servo piston, which acts to cover or uncover the slots as a means of controlling the operation of the system. This operation permits only a small amount of fluid to regulate the operation of the mechanism, which, as a result, is compact and relatively light. This mechanism is particuiarly adaptable to the drive and control of control rods in nuclear reactors. (auth)

  16. Design of mechanical joints

    CERN Document Server

    Blake, Alexander

    2018-01-01

    A cornerstone publication that covers the basic principles and practical considerations of design methodology for joints held by rivets, bolts, weld seams, and adhesive materials, Design of Mechanical Joints gives engineers the practical results and formulas they need for the preliminary design of mechanical joints, combining the essential topics of joint mechanics...strength of materials...and fracture control to provide a complete treatment of problems pertinent to the field of mechanical connections.

  17. Mechanics and thermodynamics

    CERN Document Server

    Demtröder, Wolfgang

    2017-01-01

    This introduction to classical mechanics and thermodynamics provides an accessible and clear treatment of the fundamentals. Starting with particle mechanics and an early introduction to special relativity this textbooks enables the reader to understand the basics in mechanics. The text is written from the experimental physics point of view, giving numerous real life examples and applications of classical mechanics in technology. This highly motivating presentation deepens the knowledge in a very accessible way. The second part of the text gives a concise introduction to rotational motion, an expansion to rigid bodies, fluids and gases. Finally, an extensive chapter on thermodynamics and a short introduction to nonlinear dynamics with some instructive examples intensify the knowledge of more advanced topics. Numerous problems with detailed solutions are perfect for self study.

  18. Quantum mechanics. An introduction

    International Nuclear Information System (INIS)

    Lesch, H.

    2008-01-01

    The following topics are dealt with: The way to quantum mechanics starting from thermal radiation and the stability of matter, Heisenberg's uncertainty relation, the impact of quantum mechanics on technology, the description of the big bang by means of quantum mechanics

  19. Social mechanisms and social causation

    OpenAIRE

    Friedel Weinert

    2014-01-01

    The aim of this paper is to examine the notion of social mechanisms by comparison with the notions of evolutionary and physical mechanisms. It is argued that social mechanisms are based on trends, and not lawlike regularities, so that social mechanisms are different from mechanisms in the natural sciences. Taking as an example of social causation the abolition of the slave trade, this paper argues that social mechanisms should be incorporated in Weber’s wider ...

  20. New mechanism of spiral wave initiation in a reaction-diffusion-mechanics system.

    Science.gov (United States)

    Weise, Louis D; Panfilov, Alexander V

    2011-01-01

    Spiral wave initiation in the heart muscle is a mechanism for the onset of dangerous cardiac arrhythmias. A standard protocol for spiral wave initiation is the application of a stimulus in the refractory tail of a propagating excitation wave, a region that we call the "classical vulnerable zone." Previous studies of vulnerability to spiral wave initiation did not take the influence of deformation into account, which has been shown to have a substantial effect on the excitation process of cardiomyocytes via the mechano-electrical feedback phenomenon. In this work we study the effect of deformation on the vulnerability of excitable media in a discrete reaction-diffusion-mechanics (dRDM) model. The dRDM model combines FitzHugh-Nagumo type equations for cardiac excitation with a discrete mechanical description of a finite-elastic isotropic material (Seth material) to model cardiac excitation-contraction coupling and stretch activated depolarizing current. We show that deformation alters the "classical," and forms a new vulnerable zone at longer coupling intervals. This mechanically caused vulnerable zone results in a new mechanism of spiral wave initiation, where unidirectional conduction block and rotation directions of the consequently initiated spiral waves are opposite compared to the mechanism of spiral wave initiation due to the "classical vulnerable zone." We show that this new mechanism of spiral wave initiation can naturally occur in situations that involve wave fronts with curvature, and discuss its relation to supernormal excitability of cardiac tissue. The concept of mechanically induced vulnerability may lead to a better understanding about the onset of dangerous heart arrhythmias via mechano-electrical feedback.

  1. Quantum mechanics

    CERN Document Server

    Ghosh, P K

    2014-01-01

    Quantum mechanics, designed for advanced undergraduate and graduate students of physics, mathematics and chemistry, provides a concise yet self-contained introduction to the formal framework of quantum mechanics, its application to physical problems and the interpretation of the theory. Starting with a review of some of the necessary mathematics, the basic concepts are carefully developed in the text. After building a general formalism, detailed treatment of the standard material - the harmonic oscillator, the hydrogen atom, angular momentum theory, symmetry transformations, approximation methods, identical particle and many-particle systems, and scattering theory - is presented. The concluding chapter discusses the interpretation of quantum mechanics. Some of the important topics discussed in the book are the rigged Hilbert space, deformation quantization, path integrals, coherent states, geometric phases, decoherene, etc. This book is characterized by clarity and coherence of presentation.

  2. Mechanical Restraint - Which Interventions Prevent Episodes of Mechanical Restraint? - A Systematic Review

    DEFF Research Database (Denmark)

    Bak, Jesper; Brandt-Christensen, Anne Mette; Sestoft, Dorte Maria

    2012-01-01

    PURPOSE:  To identify interventions preventing mechanical restraints. DESIGN AND METHODS:  Systematic review of international research papers dealing with mechanical restraint. The review combines qualitative and quantitative research in a new way, describing the quality of evidence and the effect...... of intervention. FINDINGS:  Implementation of cognitive milieu therapy, combined interventions, and patient-centered care were the three interventions most likely to reduce the number of mechanical restraints. PRACTICE IMPLICATIONS:  There is a lack of high-quality and effective intervention studies. This leaves...... patients and metal health professionals with uncertainty when choosing interventions in an attempt to prevent mechanical restraints....

  3. Mechanical Properties of Organic Semiconductors for Stretchable, Highly Flexible, and Mechanically Robust Electronics.

    Science.gov (United States)

    Root, Samuel E; Savagatrup, Suchol; Printz, Adam D; Rodriquez, Daniel; Lipomi, Darren J

    2017-05-10

    Mechanical deformability underpins many of the advantages of organic semiconductors. The mechanical properties of these materials are, however, diverse, and the molecular characteristics that permit charge transport can render the materials stiff and brittle. This review is a comprehensive description of the molecular and morphological parameters that govern the mechanical properties of organic semiconductors. Particular attention is paid to ways in which mechanical deformability and electronic performance can coexist. The review begins with a discussion of flexible and stretchable devices of all types, and in particular the unique characteristics of organic semiconductors. It then discusses the mechanical properties most relevant to deformable devices. In particular, it describes how low modulus, good adhesion, and absolute extensibility prior to fracture enable robust performance, along with mechanical "imperceptibility" if worn on the skin. A description of techniques of metrology precedes a discussion of the mechanical properties of three classes of organic semiconductors: π-conjugated polymers, small molecules, and composites. The discussion of each class of materials focuses on molecular structure and how this structure (and postdeposition processing) influences the solid-state packing structure and thus the mechanical properties. The review concludes with applications of organic semiconductor devices in which every component is intrinsically stretchable or highly flexible.

  4. Rod drive and latching mechanism

    International Nuclear Information System (INIS)

    Veronesi, L.; Sherwood, D.G.

    1982-01-01

    Hydraulic drive and latching mechanisms for driving reactivity control mechanisms in nuclear reactors are described. Preferably, the pressurized reactor coolant is utilized to raise the drive rod into contact with and to pivot the latching mechanism so as to allow the drive rod to pass the latching mechanism. The pressure in the housing may then be equalized which allows the drive rod to move downwardly into contact with the latching mechanism but to hold the shaft in a raised position with respect to the reactor core. Once again, the reactor coolant pressure may be utilized to raise the drive rod and thus pivot the latching mechanism so that the drive rod passes above the latching mechanism. Again, the mechanism pressure can be equalized which allows the drive rod to fall and pass by the latching mechanism so that the drive rod approaches the reactor core. (author)

  5. 1st National Mechanics Congress

    CERN Document Server

    Nieuwstadt, F

    1990-01-01

    The Department of Applied Mechanics of the Royal Institution of Engineers in the Netherlands (Koninklijk Instituut van Ingenieurs) organised on April 2-4, 1990 the first National Applied Mechanics Congress about the theme: "Integration of Theory and Applications in Applied Mechanics" The idea behind this initiative was to bring together the Applied Mechanics communities in The Netherlands and Belgium and to create an environment in which new developments in the field could be discussed and in which connections to other disciplines could be established. Among an extensive list of possible subjects the following were selected as congress topics: - non-linear material behaviour, - chaos, - mechatronics, - liquid-solid interactions, - mathematics and applied mechanics, - integration of Applied Mechanics and other disciplines. Applied Mechanics comprises both solid mechanics and fluid mechanics. These can be subdivided further into: rheology, plasticity, theory of plates and shells, theory of elasticity, multibody...

  6. Mechanisms in environmental control

    International Nuclear Information System (INIS)

    Lindeneg, K.

    1994-01-01

    The theory of implementation provides methods for decentralization of decisions in societies. By using mechanisms (game forms) it is possible (in theory) to implement attractive states in different economic environments. As an example the market mechanisms can implement Pareto-efficient and individual rational allocations in an Arrow-Debreu economic environment without market failures. And even when there exists externalities the market mechanism sometime can be used if it is possible to make a market for the goods not allocated on a market already - examples are marketable emission permits, and deposit refund systems. But environmental problems can often be explained by the existence of other market failures (e.g. asymmetric information), and then the market mechanism do not work properly. And instead of using regulation or traditional economic instruments (subsidies, charges, fees, liability insurance, marketable emission permits, or deposit refund systems) to correct the problems caused by market failures, some other methods can be used to deal with these problems. This paper contains a survey of mechanisms that can be used in environmental control when the problems are caused by the existence of public goods, externalities, asymmetric information, and indivisible goods in the economy. By examples it will be demonstrated how the Clarke-Groves mechanism, the Cournot-Lindahl mechanism, and other mechanisms can be used to solve specific environmental problems. This is only theory and examples, but a recent field study have used the Cournot-Lindahl mechanism to solve the problem of lake liming in Sweden. So this subject may be of some interests for environmental policy in the future. (au) 23 refs

  7. Noncanonical Hamiltonian mechanics

    International Nuclear Information System (INIS)

    Litteljohn, R.G.

    1986-01-01

    Noncanonical variables in Hamiltonian mechanics were first used by Lagrange in 1808. In spite of this, most work in Hamiltonian mechanics has been carried out in canonical variables, up to this day. One reason for this is that noncanonical coordinates are seldom needed for mechanical problems based on Lagrangians of the form L = T - V, where T is the kinetic energy and V is the potential energy. Of course, such Lagrangians arise naturally in celestial mechanics, and as a result they form the paradigms of nineteenth-century mechanics and have become enshrined in all the mechanics textbooks. Certain features of modern problems, however, lead to the use of noncanonical coordinates. Among these are issues of gauge invariance and singular Lagrange a Poisson structures. In addition, certain problems, like the flow of magnetic-field lines in physical space, are naturally formulated in terms of noncanonical coordinates. None of these features is present in the nineteenth-century paradigms of mechanics, but they do arise in problems involving particle motion in the presence of magnetic fields. For example, the motion of a particle in an electromagnetic wave is an important one in plasma physics, but the usual Hamiltonian formulation is gauge dependent. For this problem, noncanonical approaches based on Lagrangians in phase space lead to powerful computational techniques which are gauge invariant. In the limit of strong magnetic fields, particle motion becomes 'guiding-center motion'. Guiding-center motion is also best understood in terms of noncanonical coordinates. Finally the flow of magnetic-field lines through physical space is a Hamiltonian system which is best understood with noncanonical coordinates. No doubt many more systems will arise in the future for which these noncanonical techniques can be applied. (author)

  8. Modern logic and quantum mechanics

    International Nuclear Information System (INIS)

    Garden, R.W.

    1984-01-01

    The book applies the methods of modern logic and probabilities to ''interpreting'' quantum mechanics. The subject is described and discussed under the chapter headings: classical and quantum mechanics, modern logic, the propositional logic of mechanics, states and measurement in mechanics, the traditional analysis of probabilities, the probabilities of mechanics and the model logic of predictions. (U.K.)

  9. Methods of celestial mechanics

    CERN Document Server

    Brouwer, Dirk

    2013-01-01

    Methods of Celestial Mechanics provides a comprehensive background of celestial mechanics for practical applications. Celestial mechanics is the branch of astronomy that is devoted to the motions of celestial bodies. This book is composed of 17 chapters, and begins with the concept of elliptic motion and its expansion. The subsequent chapters are devoted to other aspects of celestial mechanics, including gravity, numerical integration of orbit, stellar aberration, lunar theory, and celestial coordinates. Considerable chapters explore the principles and application of various mathematical metho

  10. Bistable Mechanisms for Space Applications.

    Science.gov (United States)

    Zirbel, Shannon A; Tolman, Kyler A; Trease, Brian P; Howell, Larry L

    2016-01-01

    Compliant bistable mechanisms are monolithic devices with two stable equilibrium positions separated by an unstable equilibrium position. They show promise in space applications as nonexplosive release mechanisms in deployment systems, thereby eliminating friction and improving the reliability and precision of those mechanical devices. This paper presents both analytical and numerical models that are used to predict bistable behavior and can be used to create bistable mechanisms in materials not previously feasible for compliant mechanisms. Materials compatible with space applications are evaluated for use as bistable mechanisms and prototypes are fabricated in three different materials. Pin-puller and cutter release mechanisms are proposed as potential space applications.

  11. Rotary mechanical latch

    Science.gov (United States)

    Spletzer, Barry L.; Martinez, Michael A.; Marron, Lisa C.

    2012-11-13

    A rotary mechanical latch for positive latching and unlatching of a rotary device with a latchable rotating assembly having a latching gear that can be driven to latched and unlatched states by a drive mechanism such as an electric motor. A cam arm affixed to the latching gear interfaces with leading and trailing latch cams affixed to a flange within the drive mechanism. The interaction of the cam arm with leading and trailing latch cams prevents rotation of the rotating assembly by external forces such as those due to vibration or tampering.

  12. Environmental Compliance Mechanisms

    NARCIS (Netherlands)

    Merkouris, Panagiotis; Fitzmaurice, Malgosia

    2017-01-01

    Compliance mechanisms can be found in treaties regulating such diverse issues as human rights, disarmament law, and environmental law. In this bibliography, the focus will be on compliance mechanisms of multilateral environmental agreements (MEAs). Compliance with norms of international

  13. Boron atom reactions

    International Nuclear Information System (INIS)

    Estes, R.; Tabacco, M.B.; Digiuseppe, T.G.; Davidovits, P.

    1982-01-01

    The reaction rates of atomic boron with various epoxides have been measured in a flow tube apparatus. The bimolecular rate constants, in units of cm 3 molecule -1 s -1 , are: 1,2-epoxypropane (8.6 x 10 -11 ), 1,2-epoxybutane (8.8 x 10 -11 ), 1,2,3,4-diepoxybutane (5.5 x 10 -11 ), 1-chloro-2,3-epoxypropane (5.7 x 10 -11 ), and 1,2-epoxy-3,3,3-trichloropropane (1.5 x 10 -11 ). (orig.)

  14. Rearrangement and energy transfer collisions of few-body molecular systems

    International Nuclear Information System (INIS)

    Gentry, W.R.

    1981-01-01

    A great variety of experimental techniques now makes it possible to obtain dynamical information on single bimolecular collisions in a very direct way. These methods are too numerous to permit a comprehensive review in this article, but a few examples have been chosen to illustrate briefly the types of results being obtained in several areas. These include measurements of state-to-state differential cross sections for rotationally and vibrationally inelastic collisions, and rearrangement collisions studies by crossed-beam and merged-beam methods. (orig.)

  15. Tabaquismo. La naturaleza causal pide respeto

    OpenAIRE

    Chávez-Domínguez,Rafael César

    2010-01-01

    El tabaquismo es responsable de la pandemia cardiovascular mediada por aterosclerosis. Altera y acelera cambios en estructuras y funciones. Estimula factores tumorales y forma el ateroma. Induce trombosis y ocluye las arterias. La siniestra intromisión arremete contra el sistema cardiovascular. Lo daña desde sus cimientos genéticos e intimidad bimolecular. El remedio es abstención, lo resuelve todo y es sólo conducta. La adicción alimenta disentimiento que se sustenta en falacias y controvers...

  16. Selectivity in ligand recognition of G-quadruplex loops.

    Science.gov (United States)

    Campbell, Nancy H; Patel, Manisha; Tofa, Amina B; Ghosh, Ragina; Parkinson, Gary N; Neidle, Stephen

    2009-03-03

    A series of disubstituted acridine ligands have been cocrystallized with a bimolecular DNA G-quadruplex. The ligands have a range of cyclic amino end groups of varying size. The crystal structures show that the diagonal loop in this quadruplex results in a large cavity for these groups, in contrast to the steric constraints imposed by propeller loops in human telomeric quadruplexes. We conclude that the nature of the loop has a significant influence on ligand selectivity for particular quadruplex folds.

  17. Photoluminescence efficiency in AlGaN quantum wells

    Energy Technology Data Exchange (ETDEWEB)

    Tamulaitis, G.; Mickevičius, J. [Institute of Applied Research and Semiconductor Physics Department, Vilnius University, Sauletekio av. 9-III, Vilnius LT-10222 (Lithuania); Jurkevičius, J., E-mail: jonas.jurkevicius@ff.vu.lt [Institute of Applied Research and Semiconductor Physics Department, Vilnius University, Sauletekio av. 9-III, Vilnius LT-10222 (Lithuania); Shur, M.S. [Department of ECE and CIE, Rensselaer Polytechnic Institute (United States); Shatalov, M.; Yang, J.; Gaska, R. [Sensor Electronic Technology, Inc. (United States)

    2014-11-15

    Photoluminescence spectroscopy of AlGaN/AlGaN multiple quantum wells under quasi-steady-state conditions in the temperature range from 8 to 300 K revealed a strong dependence of droop onset threshold on temperature that was explained by the influence of carrier delocalization. The delocalization at room temperature results predominantly in enhancement of bimolecular radiative recombination, while being favorable for enhancement of nonradiative recombination at low temperatures. Studies of stimulated emission confirmed the strong influence of carrier localization on droop.

  18. Quenching of excited uranyl ion during its photochemical reduction by triphenylphosphine: Part III

    International Nuclear Information System (INIS)

    Sidhu, M.S.; Chahal, P.; Singh, R.J.

    1993-01-01

    Relative rates of bimolecular quenching of excited uranyl ion by some mono and di-substituted benzene derivatives have been measured during its photochemical reduction with triphenylphosphine. For the related compounds in a series it has been found that substituent groups enriching the aromatic π-electron cloud due to resonance stabilization, show an enhanced photophysical quenching action. The substituents decreasing the π-electron cloud and delocalization of positive charger over the benzene ring decrease the quenching action. (author). 16 refs., 2 figs., 1 tab

  19. Nonholonomic mechanics and control

    CERN Document Server

    Murray, RM

    2015-01-01

    This book explores some of the connections between control theory and geometric mechanics; that is, control theory is linked with a geometric view of classical mechanics in both its Lagrangian and Hamiltonian formulations and in particular with the theory of mechanical systems subject to motion constraints. The synthesis of the topic is appropriate as there is a particularly rich connection between mechanics and nonlinear control theory. The book provides a unified treatment of nonlinear control theory and constrained mechanical systems and illustrates the elegant mathematics behind many simple, interesting, and useful mechanical examples. It is intended for graduate students who wish to learn this subject and researchers in the area who want to enhance their techniques. The book contains sections focusing on physical examples and elementary terms, as well as theoretical sections that use sophisticated analysis and geometry. The first four chapters offer preliminaries and background information, while the...

  20. New mechanism of spiral wave initiation in a reaction-diffusion-mechanics system.

    Directory of Open Access Journals (Sweden)

    Louis D Weise

    Full Text Available Spiral wave initiation in the heart muscle is a mechanism for the onset of dangerous cardiac arrhythmias. A standard protocol for spiral wave initiation is the application of a stimulus in the refractory tail of a propagating excitation wave, a region that we call the "classical vulnerable zone." Previous studies of vulnerability to spiral wave initiation did not take the influence of deformation into account, which has been shown to have a substantial effect on the excitation process of cardiomyocytes via the mechano-electrical feedback phenomenon. In this work we study the effect of deformation on the vulnerability of excitable media in a discrete reaction-diffusion-mechanics (dRDM model. The dRDM model combines FitzHugh-Nagumo type equations for cardiac excitation with a discrete mechanical description of a finite-elastic isotropic material (Seth material to model cardiac excitation-contraction coupling and stretch activated depolarizing current. We show that deformation alters the "classical," and forms a new vulnerable zone at longer coupling intervals. This mechanically caused vulnerable zone results in a new mechanism of spiral wave initiation, where unidirectional conduction block and rotation directions of the consequently initiated spiral waves are opposite compared to the mechanism of spiral wave initiation due to the "classical vulnerable zone." We show that this new mechanism of spiral wave initiation can naturally occur in situations that involve wave fronts with curvature, and discuss its relation to supernormal excitability of cardiac tissue. The concept of mechanically induced vulnerability may lead to a better understanding about the onset of dangerous heart arrhythmias via mechano-electrical feedback.

  1. Control mechanisms for ecological-economic systems

    CERN Document Server

    Burkov, Vladimir N; Shchepkin, Alexander V

    2015-01-01

    This monograph presents and analyzes the optimization, game-theoretic and simulation models of control mechanisms for ecological-economic systems. It is devoted to integrated assessment mechanisms for total risks and losses, penalty mechanisms, risk payment mechanisms, financing and costs compensation mechanisms for risk level reduction, sales mechanisms for risk level quotas, audit mechanisms, mechanisms for expected losses reduction, economic motivation mechanisms, optimization mechanisms for regional environmental (risk level reduction) programs, and mechanisms for authorities' interests coordination. The book is aiming at undergraduate and postgraduate students, as well as at experts in mathematical modeling and control of ecological economic, socioeconomic and organizational systems.

  2. From fracture mechanics to damage mechanics: how to model structural deterioration

    International Nuclear Information System (INIS)

    Nicolet, S.; Lorentz, E.; Barbier, G.

    1998-01-01

    Modelling of structural deteriorations of thermo-mechanical origin is highly enhanced when using damage mechanics. Indeed, the latter offers both a fine description of the material behaviour and an ability to deal with any loading conditions, moving away the current limits of fracture mechanics. But new difficulties can arise, depending on the examined problem: if forecasts of rack initiation are well mastered, the study of crack propagation remains more complex and needs sophisticated modelizations, which are nevertheless on the point of being well understood too. (authors)

  3. Analytical mechanics

    CERN Document Server

    Helrich, Carl S

    2017-01-01

    This advanced undergraduate textbook begins with the Lagrangian formulation of Analytical Mechanics and then passes directly to the Hamiltonian formulation and the canonical equations, with constraints incorporated through Lagrange multipliers. Hamilton's Principle and the canonical equations remain the basis of the remainder of the text. Topics considered for applications include small oscillations, motion in electric and magnetic fields, and rigid body dynamics. The Hamilton-Jacobi approach is developed with special attention to the canonical transformation in order to provide a smooth and logical transition into the study of complex and chaotic systems. Finally the text has a careful treatment of relativistic mechanics and the requirement of Lorentz invariance. The text is enriched with an outline of the history of mechanics, which particularly outlines the importance of the work of Euler, Lagrange, Hamilton and Jacobi. Numerous exercises with solutions support the exceptionally clear and concise treatment...

  4. Experimental approach and micro-mechanical modeling of the mechanical behavior of irradiated zirconium alloys

    International Nuclear Information System (INIS)

    Onimus, F.

    2003-12-01

    Zirconium alloys cladding tubes containing nuclear fuel of the Pressurized Water Reactors constitute the first safety barrier against the dissemination of radioactive elements. Thus, it is essential to predict the mechanical behavior of the material in-reactor conditions. This study aims, on the one hand, to identify and characterize the mechanisms of the plastic deformation of irradiated zirconium alloys and, on the other hand, to propose a micro-mechanical modeling based on these mechanisms. The experimental analysis shows that, for the irradiated material, the plastic deformation occurs by dislocation channeling. For transverse tensile test and internal pressure test this channeling occurs in the basal planes. However, for axial tensile test, the study revealed that the plastic deformation also occurs by channeling but in the prismatic and pyramidal planes. In addition, the study of the macroscopic mechanical behavior, compared to the deformation mechanisms observed by TEM, suggested that the internal stress is higher in the case of irradiated material than in the case of non-irradiated material, because of the very heterogeneous character of the plastic deformation. This analysis led to a coherent interpretation of the mechanical behavior of irradiated materials, in terms of deformation mechanisms. The mechanical behavior of irradiated materials was finally modeled by applying homogenization methods for heterogeneous materials. This model is able to reproduce adequately the mechanical behavior of the irradiated material, in agreement with the TEM observations. (author)

  5. Axiomatic electrodynamics and microscopic mechanics

    International Nuclear Information System (INIS)

    Yussouff, M.

    1981-04-01

    A new approach to theoretical physics, along with the basic formulation of a new MICROSCOPIC MECHANICS for the motion of small charged particles is described in this set of lecture notes. Starting with the classical (Newtonian) mechanics and classical fields, the important but well known properties of Classical Electromagnetic field are discussed up to section 4. The next nection describes the usual radiation damping theory and its difficulties. It is argued that the usual treatment of radiation damping is not valid for small space and time intervals and the true description of motion requires a new type of mechanics - the MICROSCOPIC MECHANICS: Section 6 and 7 are devoted to showing that not only the new microscopic mechanics goes over to Newtonian mechanics in the proper limit, but also it is closely connected with Quantum Mechanics. All the known results of the Schroedinger theory can be reproduced by microscopic mechanics which also gives a clear physical picture. It removes Einstein's famous objections against Quantum Theory and provides a clear distinction between classical and Quantum behavior. Seven Axioms (three on Classical Mechanics, two for Maxwell's theory, one for Relativity and a new Axiom on Radiation damping) are shown to combine Classical Mechanics, Maxwellian Electrodynamics, Relativity and Schroedinger's Quantum Theory within a single theoretical framework under Microscopic Mechanics which awaits further development at the present time. (orig.)

  6. Multi-layer composite mechanical modeling for the inhomogeneous biofilm mechanical behavior.

    Science.gov (United States)

    Wang, Xiaoling; Han, Jingshi; Li, Kui; Wang, Guoqing; Hao, Mudong

    2016-08-01

    Experiments showed that bacterial biofilms are heterogeneous, for example, the density, the diffusion coefficient, and mechanical properties of the biofilm are different along the biofilm thickness. In this paper, we establish a multi-layer composite model to describe the biofilm mechanical inhomogeneity based on unified multiple-component cellular automaton (UMCCA) model. By using our model, we develop finite element simulation procedure for biofilm tension experiment. The failure limit and biofilm extension displacement obtained from our model agree well with experimental measurements. This method provides an alternative theory to study the mechanical inhomogeneity in biological materials.

  7. Comments on microscopic mechanics, generalizations of classical mechanics and Planck's oscillators

    International Nuclear Information System (INIS)

    Yussouff, M.

    1983-05-01

    The new microscopic mechanics removes the dichotomy of physics into classical and quantum phenomena. Its physical picture and connections with generalizations of classical mechanics are discussed. It gives a new meaning to Bohr's frequency relation and Planck's oscillators. (author)

  8. Mechanical stability of heat-treated nanoporous anodic alumina subjected to repetitive mechanical deformation

    Science.gov (United States)

    Bankova, A.; Videkov, V.; Tzaneva, B.; Mitov, M.

    2018-03-01

    We report studies on the mechanical response and deformation behavior of heat-treated nanoporous anodic alumina using a micro-balance test and experimental test equipment especially designed for this purpose. AAO samples were characterized mechanically by a three-point bending test using a micro-analytical balance. The deformation behavior was studied by repetitive mechanical bending of the AAO membranes using an electronically controlled system. The nanoporous AAO structures were prepared electrochemically from Al sheet substrates using a two-step anodizing technique in oxalic acid followed by heat treatment at 700 °C in air. The morphological study of the aluminum oxide layer after the mechanical tests and mechanical deformation was conducted using scanning electron and optical microscopy, respectively. The experimental results showed that the techniques proposed are simple and accurate; they could, therefore, be combined to constitute a method for mechanical stability assessment of nanostructured AAO films, which are important structural components in the design of MEMS devices and sensors.

  9. Prediction of mechanical properties for hexagonal boron nitride nanosheets using molecular mechanics model

    Energy Technology Data Exchange (ETDEWEB)

    Natsuki, Toshiaki [Shinshu University, Faculty of Textile Science and Technology, Ueda (Japan); Shinshu University, Institute of Carbon Science and Technology, Nagano (Japan); Natsuki, Jun [Shinshu University, Institute of Carbon Science and Technology, Nagano (Japan)

    2017-04-15

    Mechanical behaviors of nanomaterials are not easy to be evaluated in the laboratory because of their extremely small size and difficulty controlling. Thus, a suitable model for the estimation of the mechanical properties for nanomaterials becomes very important. In this study, the elastic properties of boron nitride (BN) nanosheets, including the elastic modulus, the shear modulus, and the Poisson's ratio, are predicted using a molecular mechanics model. The molecular mechanics force filed is established to directly incorporate the Morse potential function into the constitutive model of nanostructures. According to the molecular mechanics model, the chirality effect of hexagonal BN nanosheets on the elastic modulus is investigated through a closed-form solution. The simulated result shows that BN nanosheets exhibit an isotropic elastic property. The present analysis yields a set of very simple formulas and is able to be served as a good approximation on the mechanical properties for the BN nanosheets. (orig.)

  10. Prediction of mechanical properties for hexagonal boron nitride nanosheets using molecular mechanics model

    International Nuclear Information System (INIS)

    Natsuki, Toshiaki; Natsuki, Jun

    2017-01-01

    Mechanical behaviors of nanomaterials are not easy to be evaluated in the laboratory because of their extremely small size and difficulty controlling. Thus, a suitable model for the estimation of the mechanical properties for nanomaterials becomes very important. In this study, the elastic properties of boron nitride (BN) nanosheets, including the elastic modulus, the shear modulus, and the Poisson's ratio, are predicted using a molecular mechanics model. The molecular mechanics force filed is established to directly incorporate the Morse potential function into the constitutive model of nanostructures. According to the molecular mechanics model, the chirality effect of hexagonal BN nanosheets on the elastic modulus is investigated through a closed-form solution. The simulated result shows that BN nanosheets exhibit an isotropic elastic property. The present analysis yields a set of very simple formulas and is able to be served as a good approximation on the mechanical properties for the BN nanosheets. (orig.)

  11. Reliability design of mechanical systems a guide for mechanical and civil engineers

    CERN Document Server

    Woo, Seongwoo

    2017-01-01

    This book describes basic reliability concepts – parametric ALT plan, failure mechanism and design, and reliability testing with acceleration factor and sample size equation. A generalized life-stress failure model with a new effort concept has been derived and recommended to calculate the acceleration factor of the mechanical system. The new sample size equation with the acceleration factor has also been derived to carry out the parametric ALT. This new parametric ALT should help a mechanical/civil engineer to uncover the design parameters affecting reliability during the design process of the mechanical system. Consequently, it should help companies to improve product reliability and avoid recalls due to the product/structure failures in the field. As the improper or missing design parameters in the design phase are experimentally identified by this new reliability design method - parametric ALT, the mechanical/civil engineering system might improve in reliability by the increase in lifetime and the reduc...

  12. Chemical kinetics and reaction mechanism

    International Nuclear Information System (INIS)

    Jung, Ou Sik; Park, Youn Yeol

    1996-12-01

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

  13. Macro-mechanics controls quantum mechanics: mechanically controllable quantum conductance switching of an electrochemically fabricated atomic-scale point contact

    Science.gov (United States)

    Staiger, Torben; Wertz, Florian; Xie, Fangqing; Heinze, Marcel; Schmieder, Philipp; Lutzweiler, Christian; Schimmel, Thomas

    2018-01-01

    Here, we present a silver atomic-scale device fabricated and operated by a combined technique of electrochemical control (EC) and mechanically controllable break junction (MCBJ). With this EC-MCBJ technique, we can perform mechanically controllable bistable quantum conductance switching of a silver quantum point contact (QPC) in an electrochemical environment at room temperature. Furthermore, the silver QPC of the device can be controlled both mechanically and electrochemically, and the operating mode can be changed from ‘electrochemical’ to ‘mechanical’, which expands the operating mode for controlling QPCs. These experimental results offer the perspective that a silver QPC may be used as a contact for a nanoelectromechanical relay.

  14. Soil Mechanics

    OpenAIRE

    Verruijt, A.

    2010-01-01

    This book is the text for the introductory course of Soil Mechanics in the Department of Civil Engineering of the Delft University of Technology, as I have given from 1980 until my retirement in 2002. It contains an introduction into the major principles and methods of soil mechanics, such as the analysis of stresses, deformations, and stability. The most important methods of determining soil parameters, in the laboratory and in situ, are also described. Some basic principles of applied mecha...

  15. Computational mechanics research at ONR

    International Nuclear Information System (INIS)

    Kushner, A.S.

    1986-01-01

    Computational mechanics is not an identified program at the Office of Naval Research (ONR), but rather plays a key role in the Solid Mechanics, Fluid Mechanics, Energy Conversion, and Materials Science programs. The basic philosophy of the Mechanics Division at ONR is to support fundamental research which expands the basis for understanding, predicting, and controlling the behavior of solid and fluid materials and systems at the physical and geometric scales appropriate to the phenomena of interest. It is shown in this paper that a strong commonalty of computational mechanics drivers exists for the forefront research areas in both solid and fluid mechanics

  16. Principles of discrete time mechanics

    CERN Document Server

    Jaroszkiewicz, George

    2014-01-01

    Could time be discrete on some unimaginably small scale? Exploring the idea in depth, this unique introduction to discrete time mechanics systematically builds the theory up from scratch, beginning with the historical, physical and mathematical background to the chronon hypothesis. Covering classical and quantum discrete time mechanics, this book presents all the tools needed to formulate and develop applications of discrete time mechanics in a number of areas, including spreadsheet mechanics, classical and quantum register mechanics, and classical and quantum mechanics and field theories. A consistent emphasis on contextuality and the observer-system relationship is maintained throughout.

  17. Stochastic mechanics and quantum theory

    International Nuclear Information System (INIS)

    Goldstein, S.

    1987-01-01

    Stochastic mechanics may be regarded as both generalizing classical mechanics to processes with intrinsic randomness, as well as providing the sort of detailed description of microscopic events declared impossible under the traditional interpretation of quantum mechanics. It avoids the many conceptual difficulties which arise from the assumption that quantum mechanics, i.e., the wave function, provides a complete description of (microscopic) physical reality. Stochastic mechanics presents a unified treatment of the microscopic and macroscopic domains, in which the process of measurement plays no special physical role and which reduces to Newtonian mechanics in the macroscopic limit

  18. Theoretical physics. Quantum mechanics

    International Nuclear Information System (INIS)

    Rebhan, Eckhard

    2008-01-01

    From the first in two comprehensive volumes appeared Theoretical Physics of the author by this after Mechanics and Electrodynamics also Quantum mechanics appears as thinner single volume. First the illustrative approach via wave mechanics is reproduced. The more abstract Hilbert-space formulation introduces the author later by postulates, which are because of the preceding wave mechanics sufficiently plausible. All concepts of quantum mechanics, which contradict often to the intuitive understanding formed by macroscopic experiences, are extensively discussed and made by means of many examples as well as problems - in the largest part provided with solutions - understandable. To the interpretation of quantum mechanics an extensive special chapter is dedicated. this book arose from courses on theoretical physics, which the author has held at the Heinrich-Heine University in Duesseldorf, and was in numerous repetitions fitted to the requirement of the studyings. it is so designed that it is also after the study suited as reference book or for the renewing. All problems are very thoroughly and such extensively studied that each step is separately reproducible. About motivation and good understandability is cared much

  19. The correspondence between stochastic mechanics and quantum mechanics on multiply connected configuration spaces

    International Nuclear Information System (INIS)

    Carlen, E.A.; Loffredo, M.I.

    1989-01-01

    We show how to obtain a complete correspondence between stochastic and quantum mechanics on multiply connected spaces. We do this by introducing a stochastic mechanical analog of the hydrodynamical circulation, relating it to the topological properties of the configuration space, and using it to constrain the stochastic mechanical variational principles. (orig.)

  20. Quantum mechanics symmetries

    CERN Document Server

    Greiner, Walter

    1989-01-01

    "Quantum Dynamics" is a major survey of quantum theory based on Walter Greiner's long-running and highly successful courses at the University of Frankfurt. The key to understanding in quantum theory is to reinforce lecture attendance and textual study by working through plenty of representative and detailed examples. Firm belief in this principle led Greiner to develop his unique course and to transform it into a remarkable and comprehensive text. The text features a large number of examples and exercises involving many of the most advanced topics in quantum theory. These examples give practical and precise demonstrations of how to use the often subtle mathematics behind quantum theory. The text is divided into five volumes: Quantum Mechanics I - An Introduction, Quantum Mechanics II - Symmetries, Relativistic Quantum Mechanics, Quantum Electrodynamics, Gauge Theory of Weak Interactions. These five volumes take the reader from the fundamental postulates of quantum mechanics up to the latest research in partic...

  1. Variable mechanical ventilation.

    Science.gov (United States)

    Fontela, Paula Caitano; Prestes, Renata Bernardy; Forgiarini, Luiz Alberto; Friedman, Gilberto

    2017-01-01

    To review the literature on the use of variable mechanical ventilation and the main outcomes of this technique. Search, selection, and analysis of all original articles on variable ventilation, without restriction on the period of publication and language, available in the electronic databases LILACS, MEDLINE®, and PubMed, by searching the terms "variable ventilation" OR "noisy ventilation" OR "biologically variable ventilation". A total of 36 studies were selected. Of these, 24 were original studies, including 21 experimental studies and three clinical studies. Several experimental studies reported the beneficial effects of distinct variable ventilation strategies on lung function using different models of lung injury and healthy lungs. Variable ventilation seems to be a viable strategy for improving gas exchange and respiratory mechanics and preventing lung injury associated with mechanical ventilation. However, further clinical studies are necessary to assess the potential of variable ventilation strategies for the clinical improvement of patients undergoing mechanical ventilation.

  2. New Physical Mechanism for Lightning

    Science.gov (United States)

    Artekha, Sergey N.; Belyan, Andrey V.

    2018-02-01

    The article is devoted to electromagnetic phenomena in the atmosphere. The set of experimental data on the thunderstorm activity is analyzed. It helps to identify a possible physical mechanism of lightning flashes. This mechanism can involve the formation of metallic bonds in thunderclouds. The analysis of the problem is performed at a microphysical level within the framework of quantum mechanics. The mechanism of appearance of metallic conductivity includes the resonant tunneling of electrons along resonance-percolation trajectories. Such bonds allow the charges from the vast cloud charged subsystems concentrate quickly in lightning channel. The formation of metal bonds in the thunderstorm cloudiness is described as the second-order phase transition. A successive mechanism for the process of formation and development of the lightning channel is suggested. This mechanism is associated with the change in the orientation of crystals in growing electric field. Possible consequences of the quantum-mechanical mechanism under discussion are compared with the results of observations.

  3. p-Adic quantum mechanics

    International Nuclear Information System (INIS)

    Vladimirov, V.S.; Volovich, I.V.

    1988-01-01

    Quantum mechanics above the field of p-adic numbers is constructed. Three formulations of p-adic quantum mechanics are considered: 1) quantum mechanics with complex-valued wave functions and p-adic coordinates and pulses; an approach based on Weyl representation is suggested; 2) the probability (Euclidean) formulation; 3) the secondary quantization representation (Fock representation) with p-adic wave functions

  4. Advanced Visual Quantum Mechanics

    CERN Document Server

    Thaller, Bernd

    2005-01-01

    Advanced Visual Quantum Mechanics is a systematic effort to investigate and to teach quantum mechanics with the aid of computer-generated animations. It is a self-contained textbook that combines selected topics from atomic physics (spherical symmetry, the hydrogen atom, and particles with spin) with an introduction to quantum information theory (qubits, EPR paradox, teleportation, quantum computers). It explores relativistic quantum mechanics and the strange behavior of Dirac equation solutions. A series of appendices covers important topics from perturbation and scattering theory. The book places an emphasis on ideas and concepts, with a fair to moderate amount of mathematical rigor. Though this book stands alone, it can also be paired with Thaller Visual Quantum Mechanics to form a comprehensive course in quantum mechanics. The software for the first book earned the European Academic Software Award 2000 for outstanding innovation in its field.

  5. Mechanical properties of copper-lithium alloys produced by mechanic alloyed and hot extrusion

    International Nuclear Information System (INIS)

    Castillo B, Ricardo; Gorziglia S, Ezio; Penaloza V, Augusto

    2004-01-01

    In this work are presented the progress carried out on the characterization of some physical and mechanical properties, together with the determination of the micro mechanism of fracture of the Cu-2% wt Li, that was obtained by mechanical alloying followed hot extrusion at 500 o C and 700 o C. Hardness and tensile mechanical tests were performed together with metallographic and fractographic analysis. The experimental results obtained with powders of the Cu-Li alloy studied are compared with powder of pure copper, under similar test conditions. The results show that by hot extrusion was allowed to obtain very high densification levels for the materials under study. Moreover, it was found that lithium reduce both the tensile strength and elongation, of copper by a mechanism of embrittlement. The results are compares with the literature (au)

  6. Transient thermal-mechanical coupling behavior analysis of mechanical seals during start-up operation

    Science.gov (United States)

    Gao, B. C.; Meng, X. K.; Shen, M. X.; Peng, X. D.

    2016-05-01

    A transient thermal-mechanical coupling model for a contacting mechanical seal during start-up has been developed. It takes into consideration the coupling relationship among thermal-mechanical deformation, film thickness, temperature and heat generation. The finite element method and multi-iteration technology are applied to solve the temperature distribution and thermal-mechanical deformation as well as their evolution behavior. Results show that the seal gap transforms from negative coning to positive coning and the contact area of the mechanical seal gradually decreases during start-up. The location of the maximum temperature and maximum contact pressure move from the outer diameter to inside diameter. The heat generation and the friction torque increase sharply at first and then decrease. Meanwhile, the contact force decreases and the fluid film force and leakage rate increase.

  7. Mechanical spectral shift reactor

    International Nuclear Information System (INIS)

    Sherwood, D.G.; Wilson, J.F.; Salton, R.B.; Fensterer, H.F.

    1982-01-01

    A mechanical spectral shift reactor comprises apparatus for inserting and withdrawing water displacer elements from the reactor core for selectively changing the water-moderator volume in the core thereby changing the reactivity of the core. The apparatus includes drive mechanisms for moving the displacer elements relative to the core and guide mechanisms for guiding the displacer rods through the reactor vessel. (author)

  8. Game mechanics : advanced game design

    NARCIS (Netherlands)

    Adams, Ernest; Dormans, Joris

    2012-01-01

    Game Mechanics is aimed at game design students and industry professionals who want to improve their understanding of how to design, build, and test the mechanics of a game. Game Mechanics will show you how to design, test, and tune the core mechanics of a game—any game, from a huge role-playing

  9. Theoretical physics 2 analytical mechanics

    CERN Document Server

    Nolting, Wolfgang

    2016-01-01

    This textbook offers a clear and comprehensive introduction to analytical mechanics, one of the core components of undergraduate physics courses.It follows on naturally from the previous volumes in this series, thus expanding the knowledge in classical mechanics. The book starts with a thorough introduction into Lagrangian mechanics, detailing the d’Alembert principle, Hamilton’s principle and conservation laws. It continues with an in-depth explanation of Hamiltonian mechanics, illustrated by canonical and Legendre transformation, the generalization to quantum mechanics through Poisson brackets and all relevant variational principles. Finally, the Hamilton-Jacobi theory and the transition to wave mechanics are presented in detail. Ideally suited to undergraduate students with some grounding in classical mechanics, the book is enhanced throughout with learning features such as boxed inserts and chapter summaries, with key mathematical derivations highlighted to aid understanding. The text is supported by ...

  10. TOPOLOGICAL STRUCTURE AND MOBILITY OF THE MECHANISMS USED IN CAR MECHANICAL JACKS

    Directory of Open Access Journals (Sweden)

    Viorica VELIȘCU

    2015-05-01

    Full Text Available This paper presents a structural analysis of the mechanism of high topological type jack - screw and translator rectilinear- patina and mobility mechanism analysis using various generally applicable formulas.

  11. Mechanical seals

    CERN Document Server

    Mayer, E

    1977-01-01

    Mechanical Seals, Third Edition is a source of practical information on the design and use of mechanical seals. Topics range from design fundamentals and test rigs to leakage, wear, friction and power, reliability, and special designs. This text is comprised of nine chapters; the first of which gives a general overview of seals, including various types of seals and their applications. Attention then turns to the fundamentals of seal design, with emphasis on six requirements that must be considered: sealing effectiveness, length of life, reliability, power consumption, space requirements, and c

  12. Statistical mechanics

    CERN Document Server

    Davidson, Norman

    2003-01-01

    Clear and readable, this fine text assists students in achieving a grasp of the techniques and limitations of statistical mechanics. The treatment follows a logical progression from elementary to advanced theories, with careful attention to detail and mathematical development, and is sufficiently rigorous for introductory or intermediate graduate courses.Beginning with a study of the statistical mechanics of ideal gases and other systems of non-interacting particles, the text develops the theory in detail and applies it to the study of chemical equilibrium and the calculation of the thermody

  13. Quantum mechanics for pedestrians

    CERN Document Server

    Pade, Jochen

    2014-01-01

    This book provides an introduction into the fundamentals of non-relativistic quantum mechanics. In Part 1, the essential principles are developed. Applications and extensions of the formalism can be found in Part 2. The book includes not only material that is presented in traditional textbooks on quantum mechanics, but also discusses in detail current issues such as interaction-free quantum measurements, neutrino oscillations, various topics in the field of quantum information as well as fundamental problems and epistemological questions, such as the measurement problem, entanglement, Bell's inequality, decoherence, and the realism debate. A chapter on current interpretations of quantum mechanics concludes the book. To develop quickly and clearly the main principles of quantum mechanics and its mathematical formulation, there is a systematic change between wave mechanics and algebraic representation in the first chapters. The required mathematical tools are introduced step by step. Moreover, the appendix coll...

  14. Investigation of the Biochemical Mechanism for Cell-Substrate Mechanical Sensing

    Science.gov (United States)

    Ricotta, Vincent Anthony

    Advancements in stem cell biology and materials science have enabled the development of new treatments for tissue repair. Dental pulp stem cells (DPSCs), which are highly proliferative and can be induced to differentiate along several mesenchymal cell lineages, offer the possibility for pulpal regeneration and treatment of injured dentition. Polybutadiene (PB) may be used as a substrate for these cells. This elastomer can be spun casted into films of different thicknesses with different moduli. DPSCs grown on PB films, which are relatively hard (less than 1500 A thick), biomineralize depositing crystalline calcium phosphate without a requirement for the typical induction factor, dexamethasone (Dex). The moduli of cells track with the moduli of the surface suggesting that mechanics controls mineralization. The purpose of this study was to determine whether the major effect of Dex on biomineralization is the result of its ability to alter cell mechanics or its ability to induce osteogenesis/odontogenesis. DPSCs sense substrate mechanics through the focal adhesions, whose function is in part regulated by the Ras homolog gene (Rho) and its downstream effectors Rho associated kinases (ROCKs). ROCKs control actin filament polymerization and interactions with myosin light chain. Because cells sense substrate mechanics through focal adhesion proteins whose function is regulated by ROCKs, the impact of a ROCK inhibitor, Y-27632, was monitored. Blocking this pathway with Y-27632 suppressed the ability of DPSCs to sense the PB substrate. The cell modulus, plasma membrane stiffness, and cytosol stiffness were all lowered and biomineralization was suppressed in all cultures independent of substrate modulus or the presence of Dex. In other words, the inability of DPSCs to sense mechanical cues suppressed their ability to promote mineralization. On the other hand the expression of osteogenic/odontogenic markers (alkaline phosphatase and osteocalcin) was enhanced, perhaps due to Y

  15. Ludwig Boltzmann, mechanics and vitalism

    International Nuclear Information System (INIS)

    Broda, E.

    1990-01-01

    During most of his life Boltzmann considered classical mechanics, based on the ideas of material points and central forces, as the fundament of physics. On this basis he became one of the founders of Statistical Mechanics, through which thermodynamics was interpreted on an atomistic basis. In this work, Boltzmann was opposed by his colleague, Ernst Mach. Boltzmann also devoted much work to attempts to interpret Maxwell's theory of the electromagnetic field, of which he was a main protagonist in Central Europe, through mechanics. However, as a supporter of mechanics Boltzmann was by no means dogmatic. While he was adamant in his rejection of Wilhelm Ostwald's energism, he was openminded in respect to the relationship of mechanics, electromagnetism and atomistics. Personally, Boltzmann wanted to conserve and transmit the enormous achievements of mechanics, especially in connection with the mechanical theory of heat, so that these results should not be lost to future generations, but he encouraged attempts to proceed in new directions. While within the framework of statistical mechanics the atoms were treated like the material points of classical mechanics, Boltzmann resisted the initial, unwarranted, ideas about the structure and the properties of the atoms. When later valid ideas were evolved, Boltzmann warmly welcomed this progress, without however personally taking part in the new developments. In his later years, Boltzmann took an intense interest in biology. He supported Darwin's theories, and he contributed to them. He may be called an 'absolute Darwinist'. In his search for a natural explanation of the phenomena of life, he used the term 'mechanical', without meaning to limit them to the realm of classical mechanics. This terminological laxity is considered as unfortunate. Extending his application of Darwinian principles to advanced species, including man, Boltzmann put forward 'mechanical' explanations of thought, of morality, of the sense of beauty, and of

  16. MdCOP1 Ubiquitin E3 Ligases Interact with MdMYB1 to Regulate Light-Induced Anthocyanin Biosynthesis and Red Fruit Coloration in Apple1[W][OA

    Science.gov (United States)

    Li, Yuan-Yuan; Mao, Ke; Zhao, Cheng; Zhao, Xian-Yan; Zhang, Hua-Lei; Shu, Huai-Rui; Hao, Yu-Jin

    2012-01-01

    MdMYB1 is a crucial regulator of light-induced anthocyanin biosynthesis and fruit coloration in apple (Malus domestica). In this study, it was found that MdMYB1 protein accumulated in the light but degraded via a ubiquitin-dependent pathway in the dark. Subsequently, the MdCOP1-1 and MdCOP1-2 genes were isolated from apple fruit peel and were functionally characterized in the Arabidopsis (Arabidopsis thaliana) cop1-4 mutant. Yeast (Saccharomyces cerevisiae) two-hybrid, bimolecular fluorescence complementation, and coimmunoprecipitation assays showed that MdMYB1 interacts with the MdCOP1 proteins. Furthermore, in vitro and in vivo experiments indicated that MdCOP1s are necessary for the ubiquitination and degradation of MdMYB1 protein in the dark and are therefore involved in the light-controlled stability of the MdMYB1 protein. Finally, a viral vector-based transformation approach demonstrated that MdCOP1s negatively regulate the peel coloration of apple fruits by modulating the degradation of the MdMYB1 protein. Our findings provide new insight into the mechanism by which light controls anthocyanin accumulation and red fruit coloration in apple and even other plant species. PMID:22855936

  17. Investigation of the binding affinity in vitamin B12-Bovine serum albumin system using various spectroscopic methods

    Science.gov (United States)

    Makarska-Bialokoz, Magdalena

    2017-09-01

    The binding affinity between vitamin B12 (VitB12) and bovine serum albumin (BSA) has been investigated in aqueous solution at pH = 7.4, employing UV-vis absorption and steady-state, synchronous and three-dimensional fluorescence spectra techniques. Representative effects noted for BSA intrinsic fluorescence resulting from the interactions with VitB12 confirm the formation of π-π stacked non-covalent and non-fluorescent complexes in the system VitB12-BSA. All the determined parameters, the binding, fluorescence quenching and bimolecular quenching rate constants (of the order of 104 L mol- 1, 103 L mol- 1 and 1011 L mol- 1 s- 1, respectively), as well as Förster resonance energy transfer parameters validate the mechanism of static quenching. The interaction with VitB12 induces folding of the polypeptide chains around Trp residues of BSA, resulting in a more hydrophobic surrounding. Presented outcomes suggest that the addition of VitB12 can lead to the more organized BSA conformation and its more folded tertiary structure, what could influence the physiological functions of bovine serum albumin, notably in case of its overuse or abnormal metabolism.

  18. Bleaching of cotton fabric with tetraacetylhydrazine as bleach activator for H2O2.

    Science.gov (United States)

    Liu, Kai; Zhang, Xuan; Yan, Kelu

    2018-05-15

    Tetraacetylhydrazine (TH) as bleach activator for H 2 O 2 cotton bleaching was synthesized and characterized by 1 H NMR, 13 C NMR and MS spectra. TH has better solubility than that of TAED. The CIE whiteness index (WI), H 2 O 2 decomposition rate and bursting strength were employed to investigate the performance of H 2 O 2 /TH bleaching system. By addition of TH, WI and H 2 O 2 decomposition rate increased significantly at 70 °C. Bleaching temperature, NaHCO 3 concentration and bleaching time were also discussed in detail and the loss of bursting strength is not clear. By using benzenepentacarboxylic acid (BA) as a fluorescent probe for hydroxyl radical detection, the bleaching process of H 2 O 2 /TH system was investigated. Acetylhydrazine and diacetylhydrazine were also utilized to further confirm the process. In addition, bimolecular decomposition was investigated by using 9,10-dimethylanthracene (DMA) as fluorescent probe of 1 O 2 . Based on these experimental results, the bleaching mechanism of H 2 O 2 /TH system was proposed. Copyright © 2018 Elsevier Ltd. All rights reserved.

  19. Allosteric interactions between agonists and antagonists within the adenosine A2A receptor-dopamine D2 receptor heterotetramer.

    Science.gov (United States)

    Bonaventura, Jordi; Navarro, Gemma; Casadó-Anguera, Verònica; Azdad, Karima; Rea, William; Moreno, Estefanía; Brugarolas, Marc; Mallol, Josefa; Canela, Enric I; Lluís, Carme; Cortés, Antoni; Volkow, Nora D; Schiffmann, Serge N; Ferré, Sergi; Casadó, Vicent

    2015-07-07

    Adenosine A2A receptor (A2AR)-dopamine D2 receptor (D2R) heteromers are key modulators of striatal neuronal function. It has been suggested that the psychostimulant effects of caffeine depend on its ability to block an allosteric modulation within the A2AR-D2R heteromer, by which adenosine decreases the affinity and intrinsic efficacy of dopamine at the D2R. We describe novel unsuspected allosteric mechanisms within the heteromer by which not only A2AR agonists, but also A2AR antagonists, decrease the affinity and intrinsic efficacy of D2R agonists and the affinity of D2R antagonists. Strikingly, these allosteric modulations disappear on agonist and antagonist coadministration. This can be explained by a model that considers A2AR-D2R heteromers as heterotetramers, constituted by A2AR and D2R homodimers, as demonstrated by experiments with bioluminescence resonance energy transfer and bimolecular fluorescence and bioluminescence complementation. As predicted by the model, high concentrations of A2AR antagonists behaved as A2AR agonists and decreased D2R function in the brain.

  20. Conformational Analysis of Misfolded Protein Aggregation by FRET and Live-Cell Imaging Techniques

    Directory of Open Access Journals (Sweden)

    Akira Kitamura

    2015-03-01

    Full Text Available Cellular homeostasis is maintained by several types of protein machinery, including molecular chaperones and proteolysis systems. Dysregulation of the proteome disrupts homeostasis in cells, tissues, and the organism as a whole, and has been hypothesized to cause neurodegenerative disorders, including amyotrophic lateral sclerosis (ALS and Huntington’s disease (HD. A hallmark of neurodegenerative disorders is formation of ubiquitin-positive inclusion bodies in neurons, suggesting that the aggregation process of misfolded proteins changes during disease progression. Hence, high-throughput determination of soluble oligomers during the aggregation process, as well as the conformation of sequestered proteins in inclusion bodies, is essential for elucidation of physiological regulation mechanism and drug discovery in this field. To elucidate the interaction, accumulation, and conformation of aggregation-prone proteins, in situ spectroscopic imaging techniques, such as Förster/fluorescence resonance energy transfer (FRET, fluorescence correlation spectroscopy (FCS, and bimolecular fluorescence complementation (BiFC have been employed. Here, we summarize recent reports in which these techniques were applied to the analysis of aggregation-prone proteins (in particular their dimerization, interactions, and conformational changes, and describe several fluorescent indicators used for real-time observation of physiological states related to proteostasis.

  1. The fate of primary cations in radiolysis of alkanes as studied by ESR

    International Nuclear Information System (INIS)

    Iwasaki, M.; Toriyama, K.; Nunome, K.

    1983-01-01

    The structures and reactions of alkane cations (RH + ) have been studied by ESR to elucidate the fate of primary cations in radiolysis of alkanes. Radical cations of prototype alkanes such as C 2 H 6 , C 3 H 8 , iso-C 4 H 10 and neo-C 5 H 12 etc. as well as their partially deuterated analogues were stabilized in irradiated frozen matrices such as SF 6 , CFCl 2 CF 2 Cl and CFCl 3 having a higher ionization potential than that of these alkanes contained as dilute solutes. RH + in SF 6 and in CFCl 2 CF 2 Cl converts into alkyl radicals by deprotonation probably through bimolecular reactions, whereas RH + in CFCl 3 unimolecularily decomposes into olefinic cations by H 2 and/or CH 4 elimination reactions. It is further found that the electronic structures of propane and isobutane cations in halocarbon matrices are different from those in SF 6 and the difference is drastically reflected in the site preference of their deprotonation reactions. The results are discussed in relation to the mechanisms of pairwise formation of alkyl radicals in low temperature radiolysis of neat alkanes and its suppression by addition of electron scavengers. (author)

  2. Tautomerization and Dimerization of 6,13-Disubstituted Derivatives of Pentacene.

    Science.gov (United States)

    Garcia-Borràs, Marc; Konishi, Akihito; Waterloo, Andreas; Liang, Yong; Cao, Yang; Hetzer, Constantin; Lehnherr, Dan; Hampel, Frank; Houk, Kendall N; Tykwinski, Rik R

    2017-05-02

    Two new 6,13-disubstituted pentacene derivatives, 1 c and 1 d, with alkyl and triisopropylsilylethynyl substitution have been synthesized and characterized experimentally and computationally. The alkyl substituted 1 c and 1 d represent the first 6-alkyl-substituted pentacene derivative where the fully aromatic species dominates over the corresponding tautomer. Indeed, no tautomerization product is found for either 1 c or 1 d upon heating or in the presence of catalytic amounts of acid. On the other hand, an unexpected dimer (3 c) is formed from 1 c. A plausible mechanism for this new dimerization process of the 6-methyl-substituted pentacene derivative 1 c is proposed, which involves first a bimolecular hydrogen atom transfer followed by an intramolecular [4+2] Diels-Alder cycloaddition. In the case of 6-butyl substitution, neither tautomerization nor dimerization is observed. Computations support the proposed 1 c dehydrodimerization pathway, explain why 1 d does not dimerize, and show the importance of the nature of the group at C-13 in controlling the relative stability of 6-alkyl-substituted pentacene tautomers. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. RNAstructure: software for RNA secondary structure prediction and analysis.

    Science.gov (United States)

    Reuter, Jessica S; Mathews, David H

    2010-03-15

    To understand an RNA sequence's mechanism of action, the structure must be known. Furthermore, target RNA structure is an important consideration in the design of small interfering RNAs and antisense DNA oligonucleotides. RNA secondary structure prediction, using thermodynamics, can be used to develop hypotheses about the structure of an RNA sequence. RNAstructure is a software package for RNA secondary structure prediction and analysis. It uses thermodynamics and utilizes the most recent set of nearest neighbor parameters from the Turner group. It includes methods for secondary structure prediction (using several algorithms), prediction of base pair probabilities, bimolecular structure prediction, and prediction of a structure common to two sequences. This contribution describes new extensions to the package, including a library of C++ classes for incorporation into other programs, a user-friendly graphical user interface written in JAVA, and new Unix-style text interfaces. The original graphical user interface for Microsoft Windows is still maintained. The extensions to RNAstructure serve to make RNA secondary structure prediction user-friendly. The package is available for download from the Mathews lab homepage at http://rna.urmc.rochester.edu/RNAstructure.html.

  4. Some connections between relativistic classical mechanics, statistical mechanics, and quantum field theory

    International Nuclear Information System (INIS)

    Remler, E.A.

    1977-01-01

    A gauge-invariant version of the Wigner representation is used to relate relativistic mechanics, statistical mechanics, and quantum field theory in the context of the electrodynamics of scalar particles. A unified formulation of quantum field theory and statistical mechanics is developed which clarifies the physics interpretation of the single-particle Wigner function. A covariant form of Ehrenfest's theorem is derived. Classical electrodynamics is derived from quantum field theory after making a random-phase approximation. The validity of this approximation is discussed

  5. Designing an optimally proportional inorganic scintillator

    Energy Technology Data Exchange (ETDEWEB)

    Singh, Jai, E-mail: jai.singh@cdu.edu.au [School of Engineering and IT, B-Purple-12, Faculty of EHSE, Charles Darwin University, NT 0909 (Australia); Koblov, Alexander [School of Engineering and IT, B-Purple-12, Faculty of EHSE, Charles Darwin University, NT 0909 (Australia)

    2012-09-01

    The nonproportionality observed in the light yield of inorganic scintillators is studied theoretically as a function of the rates of bimolecular and Auger quenching processes occurring within the electron track initiated by a gamma- or X-ray photon incident on a scintillator. Assuming a cylindrical track, the influence of the track radius and concentration of excitations created within the track on the scintillator light yield is also studied. Analysing the calculated light yield a guideline for inventing an optimally proportional scintillator with optimal energy resolution is presented.

  6. Designing an optimally proportional inorganic scintillator

    International Nuclear Information System (INIS)

    Singh, Jai; Koblov, Alexander

    2012-01-01

    The nonproportionality observed in the light yield of inorganic scintillators is studied theoretically as a function of the rates of bimolecular and Auger quenching processes occurring within the electron track initiated by a gamma- or X-ray photon incident on a scintillator. Assuming a cylindrical track, the influence of the track radius and concentration of excitations created within the track on the scintillator light yield is also studied. Analysing the calculated light yield a guideline for inventing an optimally proportional scintillator with optimal energy resolution is presented.

  7. Multipoint attachment to a support protects enzyme from inactivation by organic solvents: alpha-Chymotrypsin in aqueous solutions of alcohols and diols.

    Science.gov (United States)

    Mozhaev, V V; Sergeeva, M V; Belova, A B; Khmelnitsky, Y L

    1990-03-25

    Inactivation of alpha-chymotrypsin in aqueous solutions of alcohols and diols proceeds both reversibly and irreversibly. Reversible loss of the specific enzyme activity results from conformational changes (unfolding) of the enzyme detected by fluorescence spectroscopy. Multipoint covalent attachment to the matrix of polyacryl-amide gel by copolymerization method stabilizes alpha-chymotrypsin from denaturation by alcohols, the stabilizing effect increasing with the number of bonds between the protein and the support. Immobilization protects the enzyme also from irreversible inactivation by organic solvents resulting from bimolecular aggregation and autolysis.

  8. Quantum Control of Molecular Processes

    CERN Document Server

    Shapiro, Moshe

    2012-01-01

    Written by two of the world's leading researchers in the field, this is a systematic introduction to the fundamental principles of coherent control, and to the underlying physics and chemistry.This fully updated second edition is enhanced by 80% and covers the latest techniques and applications, including nanostructures, attosecond processes, optical control of chirality, and weak and strong field quantum control. Developments and challenges in decoherence-sensitive condensed phase control as well as in bimolecular control are clearly described.Indispensable for atomic, molecular and chemical

  9. Hybrid dynamic modeling of Escherichia coli central metabolic network combining Michaelis–Menten and approximate kinetic equations

    DEFF Research Database (Denmark)

    Costa, Rafael S.; Machado, Daniel; Rocha, Isabel

    2010-01-01

    , represent nowadays the limiting factor in the construction of such models. In this study, we compare four alternative modeling approaches based on Michaelis–Menten kinetics for the bi-molecular reactions and different types of simplified rate equations for the remaining reactions (generalized mass action......The construction of dynamic metabolic models at reaction network level requires the use of mechanistic enzymatic rate equations that comprise a large number of parameters. The lack of knowledge on these equations and the difficulty in the experimental identification of their associated parameters...

  10. Quantum mechanics as classical statistical mechanics with an ontic extension and an epistemic restriction.

    Science.gov (United States)

    Budiyono, Agung; Rohrlich, Daniel

    2017-11-03

    Where does quantum mechanics part ways with classical mechanics? How does quantum randomness differ fundamentally from classical randomness? We cannot fully explain how the theories differ until we can derive them within a single axiomatic framework, allowing an unambiguous account of how one theory is the limit of the other. Here we derive non-relativistic quantum mechanics and classical statistical mechanics within a common framework. The common axioms include conservation of average energy and conservation of probability current. But two axioms distinguish quantum mechanics from classical statistical mechanics: an "ontic extension" defines a nonseparable (global) random variable that generates physical correlations, and an "epistemic restriction" constrains allowed phase space distributions. The ontic extension and epistemic restriction, with strength on the order of Planck's constant, imply quantum entanglement and uncertainty relations. This framework suggests that the wave function is epistemic, yet it does not provide an ontic dynamics for individual systems.

  11. Word learning mechanisms.

    Science.gov (United States)

    He, Angela Xiaoxue; Arunachalam, Sudha

    2017-07-01

    How do children acquire the meanings of words? Many word learning mechanisms have been proposed to guide learners through this challenging task. Despite the availability of rich information in the learner's linguistic and extralinguistic input, the word-learning task is insurmountable without such mechanisms for filtering through and utilizing that information. Different kinds of words, such as nouns denoting object concepts and verbs denoting event concepts, require to some extent different kinds of information and, therefore, access to different kinds of mechanisms. We review some of these mechanisms to examine the relationship between the input that is available to learners and learners' intake of that input-that is, the organized, interpreted, and stored representations they form. We discuss how learners segment individual words from the speech stream and identify their grammatical categories, how they identify the concepts denoted by these words, and how they refine their initial representations of word meanings. WIREs Cogn Sci 2017, 8:e1435. doi: 10.1002/wcs.1435 This article is categorized under: Linguistics > Language Acquisition Psychology > Language. © 2017 Wiley Periodicals, Inc.

  12. Mechanisms of sintering

    International Nuclear Information System (INIS)

    Mohan, Ashok; Soni, N.C.; Moorthy, V.K.

    1980-01-01

    The basic mechanisms by which the material moves during sintering have not only held a strange fascination but are also very important in determining the properties of the end product. Kuczynski's exponent method has been subsequently refined by several schools to make it increasingly reliable. There is now a fairly good understanding of mechanisms in some of the materials. However in others the issue is complicated by their basic nature. The problems of ambiguity in criterion and that of more than one mechanism being simultaneously operative have been tackled with dexterity by Ashby for drawing sintering mechanism diagrams. The method has been modified to give Relative Contribution Diagrams (RCD). These yield additional information and have been used for analysis. The main criticism against this is that it uses a very large number of rate equations and material properties, which can communicate their inaccuracies to the diagram. A case study of UO 2 was undertaken and it has been shown quantitatively that inaccuracies in a smaller number of properties only affect the diagrams to any significant extent. (auth.)

  13. Impact Mechanics

    Science.gov (United States)

    Stronge, W. J.

    2004-03-01

    Impact mechanics is concerned with the reaction forces that develop during a collision and the dynamic response of structures to these reaction forces. The subject has a wide range of engineering applications, from designing sports equipment to improving the crashworthiness of automobiles. This book develops several different methodologies for analysing collisions between structures. These range from rigid body theory for structures that are stiff and compact, to vibration and wave analyses for flexible structures. The emphasis is on low-speed impact where damage is local to the small region of contact between the colliding bodies. The analytical methods presented give results that are more robust or less sensitive to initial conditions than have been achieved hitherto. As a text, Impact Mechanics builds upon foundation courses in dynamics and strength of materials. It includes numerous industrially relevant examples and end-of-chapter homework problems drawn from industry and sports. Practising engineers will also find the methods presented in this book useful in calculating the response of a mechanical system to impact.

  14. Study on AE in Mechanical Seal Lift-off Recognition of Mechanical Main Shaft

    Directory of Open Access Journals (Sweden)

    Erqing Zhang

    2014-06-01

    Full Text Available For the problem of the determination of lift-off position and the measurement of end face thickness for mechanical seal more difficult, the method based on acoustic emission signal end face lift-off condition monitoring technology for mechanical seal was proposed. The electric eddy current sensor made direct measurement in the internal of mechanical seal device, and the acoustic emission sensor was fixed in the outside for indirect measurement. The acoustic emission signals were de-noised by wavelet threshold de-noising method. The representative energy features were selected by wavelet packet energy spectrum algorithm. It was established that the Radial Basis Function neural network model used for identification of the mechanical seal lift-off position, and the extracted wavelet energy features as its input. It was confirmed accurate and effective that the acoustic emission identification technology through comparing with the data detected by electric eddy current sensor. So using the acoustic emission technology realized the identification of the mechanical seal lift-off position of mechanical main shaft from inside to outside. It is convenient to be used and promotion in industrial field.

  15. How to recover Newtonian mechanics from non-relative quantum mechanics in limit ℎ→0

    International Nuclear Information System (INIS)

    Mei Shizhong

    2001-01-01

    It is assumed that when ℎ→0, correct non-relative quantum mechanics should be equivalent to Newtonian mechanics. Starting from this point, the authors slightly revised the widely accepted non-relative quantum mechanics such that the mechanics after modification is strictly equivalent to that before the modification when ℎ≠0, and equivalent to Newtonian mechanics in the limit ℎ→0. The significance lies in the possibility that if authors further postulate that corrected relative quantum mechanics is equivalent to Einstein's theory of relativity in the case ℎ→0, then authors may obtain different predictions from what produced by the former that will help to verify or improve it

  16. A constitutive mechanical model for gas hydrate bearing sediments incorporating inelastic mechanisms

    KAUST Repository

    Sá nchez, Marcelo; Gai, Xuerui; Santamarina, Carlos

    2016-01-01

    , hydrates dissociate and move from the solid to the gas phase. Hydrate dissociation is accompanied by significant changes in sediment structure and strongly affects its mechanical behavior (e.g., sediment stiffenss, strength and dilatancy). The mechanical

  17. Introduction to contact mechanics

    CERN Document Server

    Fischer-Cripps, Anthony C

    2000-01-01

    Contact mechanics deals with the elastic or plastic contact between two solid objects, and is thus intimately connected with such topics as fracture, hardness, and elasticity.This text, intended for advanced undergraduates, begins with an introduction to the mechanical properties of materials, general fracture mechanics, and fractures in brittle solids.This is followed by a detailed discussion of stresses and the nature of elastic and elastic-plastic contact.

  18. Fluid mechanics of heart valves.

    Science.gov (United States)

    Yoganathan, Ajit P; He, Zhaoming; Casey Jones, S

    2004-01-01

    Valvular heart disease is a life-threatening disease that afflicts millions of people worldwide and leads to approximately 250,000 valve repairs and/or replacements each year. Malfunction of a native valve impairs its efficient fluid mechanic/hemodynamic performance. Artificial heart valves have been used since 1960 to replace diseased native valves and have saved millions of lives. Unfortunately, despite four decades of use, these devices are less than ideal and lead to many complications. Many of these complications/problems are directly related to the fluid mechanics associated with the various mechanical and bioprosthetic valve designs. This review focuses on the state-of-the-art experimental and computational fluid mechanics of native and prosthetic heart valves in current clinical use. The fluid dynamic performance characteristics of caged-ball, tilting-disc, bileaflet mechanical valves and porcine and pericardial stented and nonstented bioprostheic valves are reviewed. Other issues related to heart valve performance, such as biomaterials, solid mechanics, tissue mechanics, and durability, are not addressed in this review.

  19. Advances in Soft Matter Mechanics

    CERN Document Server

    Li, Shaofan

    2012-01-01

    "Advances in Soft Matter Mechanics" is a compilation and selection of recent works in soft matter mechanics by a group of active researchers in the field. The main objectives of this book are first to disseminate the latest developments in soft matter mechanics in the field of applied and computational mechanics, and second to introduce soft matter mechanics as a sub-discipline of soft matter physics. As an important branch of soft matter physics, soft matter mechanics has developed rapidly in recent years. A number of the novel approaches discussed in this book are unique, such as the coarse grained finite element method for modeling colloidal adhesion, entropic elasticity, meshfree simulations of liquid crystal elastomers, simulations of DNA, etc. The book is intended for researchers and graduate students in the field of mechanics, condensed matter physics and biomaterials. Dr. Shaofan Li is a professor of the University of California-Berkeley, U.S.A; Dr. Bohua Sun is a professor of Cape Peninsula Universit...

  20. Questioning quantum mechanics

    Science.gov (United States)

    Frappier, Mélanie

    2018-03-01

    A century after its inception, quantum mechanics continues to puzzle us with dead-and-alive cats, waves "collapsing" into particles, and "spooky action at a distance." In his first book, What Is Real?, science writer and astrophysicist Adam Becker sets out to explore why the physics community is still arguing today about quantum mechanics's true meaning.

  1. Effect of Mechanical Alloying Atmospheres and Oxygen Concentration on Mechanical Properties of ODS Ferritic Steels

    International Nuclear Information System (INIS)

    Noh, Sanghoon; Choi, Byoungkwon; Han, Changhee; Kim, Kibaik; Kang, Sukhoon; Chun, Youngbum; Kim, Taekyu

    2013-01-01

    Finely dispersed nano-oxide particles with a high number density in the homogeneous grain matrix are essential to achieve superior mechanical properties at high temperatures, and these unique microstructures can be obtained through the mechanical alloying (MA) and hot consolidation process. The microstructure and mechanical property of ODS steel significantly depends on its powder property and the purity after the MA process. These contents should be carefully controlled to improve the mechanical property at elevated temperature. In particular, appropriate the control of oxygen concentration improves the mechanical property of ODS steel at high temperature. An effective method is to control the mechanical alloying atmosphere by high purity inert gas. In the present study, the effects of mechanical alloying atmospheres and oxygen concentration on the mechanical property of ODS steel were investigated. ODS ferritic alloys were fabricated in various atmospheres, and the HIP process was used to investigate the effects of MA atmospheres and oxygen concentration on the microstructure and mechanical property. ODS ferritic alloys milled in an Ar-H 2 mixture, and He is effective to reduce the excess oxygen concentration. The YH 2 addition made an extremely reduced oxygen concentration by the internal oxygen reduction reaction and resulted in a homogeneous microstructure and superior creep strength

  2. Classicality in quantum mechanics

    Energy Technology Data Exchange (ETDEWEB)

    Dreyer, Olaf [Theoretical Physics, Blackett Laboratory, Imperial College London, London, SW7 2AZ (United Kingdom)

    2007-05-15

    In this article we propose a solution to the measurement problem in quantum mechanics. We point out that the measurement problem can be traced to an a priori notion of classicality in the formulation of quantum mechanics. If this notion of classicality is dropped and instead classicality is defined in purely quantum mechanical terms the measurement problem can be avoided. We give such a definition of classicality. It identifies classicality as a property of large quantum system. We show how the probabilistic nature of quantum mechanics is a result of this notion of classicality. We also comment on what the implications of this view are for the search of a quantum theory of gravity.

  3. Classicality in quantum mechanics

    International Nuclear Information System (INIS)

    Dreyer, Olaf

    2007-01-01

    In this article we propose a solution to the measurement problem in quantum mechanics. We point out that the measurement problem can be traced to an a priori notion of classicality in the formulation of quantum mechanics. If this notion of classicality is dropped and instead classicality is defined in purely quantum mechanical terms the measurement problem can be avoided. We give such a definition of classicality. It identifies classicality as a property of large quantum system. We show how the probabilistic nature of quantum mechanics is a result of this notion of classicality. We also comment on what the implications of this view are for the search of a quantum theory of gravity

  4. Trace of Korean mechanical industry

    International Nuclear Information System (INIS)

    1996-12-01

    This book reports 50 years of Korean mechanical engineers, which includes birth and history, remembrance and future of Korean society of mechanical engineers, current situation and development of mechanical industry such as national industry and 50 years of mechanical industry, track, airline industry, ship and marine engine, a precision instrument, cutting work, casting, welding, plastic working freeze and air handling nuclear power and textile machinery.

  5. Accelerated testing of space mechanisms

    Science.gov (United States)

    Murray, S. Frank; Heshmat, Hooshang

    1995-01-01

    This report contains a review of various existing life prediction techniques used for a wide range of space mechanisms. Life prediction techniques utilized in other non-space fields such as turbine engine design are also reviewed for applicability to many space mechanism issues. The development of new concepts on how various tribological processes are involved in the life of the complex mechanisms used for space applications are examined. A 'roadmap' for the complete implementation of a tribological prediction approach for complex mechanical systems including standard procedures for test planning, analytical models for life prediction and experimental verification of the life prediction and accelerated testing techniques are discussed. A plan is presented to demonstrate a method for predicting the life and/or performance of a selected space mechanism mechanical component.

  6. Mathematical modelling in solid mechanics

    CERN Document Server

    Sofonea, Mircea; Steigmann, David

    2017-01-01

    This book presents new research results in multidisciplinary fields of mathematical and numerical modelling in mechanics. The chapters treat the topics: mathematical modelling in solid, fluid and contact mechanics nonconvex variational analysis with emphasis to nonlinear solid and structural mechanics numerical modelling of problems with non-smooth constitutive laws, approximation of variational and hemivariational inequalities, numerical analysis of discrete schemes, numerical methods and the corresponding algorithms, applications to mechanical engineering numerical aspects of non-smooth mechanics, with emphasis on developing accurate and reliable computational tools mechanics of fibre-reinforced materials behaviour of elasto-plastic materials accounting for the microstructural defects definition of structural defects based on the differential geometry concepts or on the atomistic basis interaction between phase transformation and dislocations at nano-scale energetic arguments bifurcation and post-buckling a...

  7. Supersymmetry and quantum mechanics

    International Nuclear Information System (INIS)

    Cooper, F.; Sukhatme, U.

    1995-01-01

    In the past ten years, the ideas of supersymmetry have been profitably applied to many nonrelativistic quantum mechanical problems. In particular, there is now a much deeper understanding of why certain potentials are analytically solvable and an array of powerful new approximation methods for handling potentials which are not exactly solvable. In this report, we review the theoretical formulation of supersymmetric quantum mechanics and discuss many applications. Exactly solvable potentials can be understood in terms of a few basic ideas which include supersymmetric partner potentials, shape invariance and operator transformations. Familiar solvable potentials all have the property of shape invariance. We describe new exactly solvable shape invariant potentials which include the recently discovered self-similar potentials as a special case. The connection between inverse scattering, isospectral potentials and supersymmetric quantum mechanics is discussed and multi-soliton solutions of the KdV equation are constructed. Approximation methods are also discussed within the framework of supersymmetric quantum mechanics and in particular it is shown that a supersymmetry inspired WKB approximation is exact for a class of shape invariant potentials. Supersymmetry ideas give particularly nice results for the tunneling rate in a double well potential and for improving large N expansions. We also discuss the problem of a charged Dirac particle in an external magnetic field and other potentials in terms of supersymmetric quantum mechanics. Finally, we discuss structures more general than supersymmetric quantum mechanics such as parasupersymmetric quantum mechanics in which there is a symmetry between a boson and a para-fermion of order p. ((orig.))

  8. Nuclear Mechanics and Stem Cell Differentiation.

    Science.gov (United States)

    Mao, Xinjian; Gavara, Nuria; Song, Guanbin

    2015-12-01

    Stem cells are characterized by their self-renewal and multi-lineage differentiation potential. Stem cell differentiation is a prerequisite for the application of stem cells in regenerative medicine and clinical therapy. In addition to chemical stimulation, mechanical cues play a significant role in regulating stem cell differentiation. The integrity of mechanical sensors is necessary for the ability of cells to respond to mechanical signals. The nucleus, the largest and stiffest cellular organelle, interacts with the cytoskeleton as a key mediator of cell mechanics. Nuclear mechanics are involved in the complicated interactions of lamins, chromatin and nucleoskeleton-related proteins. Thus, stem cell differentiation is intimately associated with nuclear mechanics due to its indispensable role in mechanotransduction and mechanical response. This paper reviews several main contributions of nuclear mechanics, highlights the hallmarks of the nuclear mechanics of stem cells, and provides insight into the relationship between nuclear mechanics and stem cell differentiation, which may guide clinical applications in the future.

  9. Simulation with quantum mechanics/molecular mechanics for drug discovery.

    Science.gov (United States)

    Barbault, Florent; Maurel, François

    2015-10-01

    Biological macromolecules, such as proteins or nucleic acids, are (still) molecules and thus they follow the same chemical rules that any simple molecule follows, even if their size generally renders accurate studies unhelpful. However, in the context of drug discovery, a detailed analysis of ligand association is required for understanding or predicting their interactions and hybrid quantum mechanics/molecular mechanics (QM/MM) computations are relevant tools to help elucidate this process. In this review, the authors explore the use of QM/MM for drug discovery. After a brief description of the molecular mechanics (MM) technique, the authors describe the subtractive and additive techniques for QM/MM computations. The authors then present several application cases in topics involved in drug discovery. QM/MM have been widely employed during the last decades to study chemical processes such as enzyme-inhibitor interactions. However, despite the enthusiasm around this area, plain MM simulations may be more meaningful than QM/MM. To obtain reliable results, the authors suggest fixing several keystone parameters according to the underlying chemistry of each studied system.

  10. Symmetries in discrete-time mechanics

    International Nuclear Information System (INIS)

    Khorrami, M.

    1996-01-01

    Based on a general formulation for discrete-time quantum mechanics, introduced by M. Khorrami (Annals Phys. 224 (1995), 101), symmetries in discrete-time quantum mechanics are investigated. It is shown that any classical continuous symmetry leads to a conserved quantity in classical mechanics, as well as quantum mechanics. The transformed wave function, however, has the correct evolution if and only if the symmetry is nonanomalous. Copyright copyright 1996 Academic Press, Inc

  11. Contact Hamiltonian mechanics

    Energy Technology Data Exchange (ETDEWEB)

    Bravetti, Alessandro, E-mail: alessandro.bravetti@iimas.unam.mx [Instituto de Investigaciones en Matemáticas Aplicadas y en Sistemas, Universidad Nacional Autónoma de México, A. P. 70543, México, DF 04510 (Mexico); Cruz, Hans, E-mail: hans@ciencias.unam.mx [Instituto de Ciencias Nucleares, Universidad Nacional Autónoma de México, A. P. 70543, México, DF 04510 (Mexico); Tapias, Diego, E-mail: diego.tapias@nucleares.unam.mx [Facultad de Ciencias, Universidad Nacional Autónoma de México, A.P. 70543, México, DF 04510 (Mexico)

    2017-01-15

    In this work we introduce contact Hamiltonian mechanics, an extension of symplectic Hamiltonian mechanics, and show that it is a natural candidate for a geometric description of non-dissipative and dissipative systems. For this purpose we review in detail the major features of standard symplectic Hamiltonian dynamics and show that all of them can be generalized to the contact case.

  12. A pseudobond parametrization for improved electrostatics in quantum mechanical/molecular mechanical simulations of enzymes.

    Science.gov (United States)

    Parks, Jerry M; Hu, Hao; Cohen, Aron J; Yang, Weitao

    2008-10-21

    The pseudobond method is used in quantum mechanical/molecular mechanical (QM/MM) simulations in which a covalent bond connects the quantum mechanical and classical subsystems. In this method, the molecular mechanical boundary atom is replaced by a special quantum mechanical atom with one free valence that forms a bond with the rest of the quantum mechanical subsystem. This boundary atom is modified through the use of a parametrized effective core potential and basis set. The pseudobond is designed to reproduce the properties of the covalent bond that it has replaced, while invoking as small a perturbation as possible on the system. Following the work of Zhang [J. Chem. Phys. 122, 024114 (2005)], we have developed new pseudobond parameters for use in the simulation of enzymatic systems. Our parameters yield improved electrostatics and deprotonation energies, while at the same time maintaining accurate geometries. We provide parameters for C(ps)(sp(3))-C(sp(3)), C(ps)(sp(3))-C(sp(2),carbonyl), and C(ps)(sp(3))-N(sp(3)) pseudobonds, which allow the interface between the quantum mechanical and molecular mechanical subsystems to be constructed at either the C(alpha)-C(beta) bond of a given amino acid residue or along the peptide backbone. In addition, we demonstrate the efficiency of our parametrization method by generating residue-specific pseudobond parameters for a single amino acid. Such an approach may enable higher accuracy than general purpose parameters for specific QM/MM applications.

  13. Prologue to super quantum mechanics something is rotten in the state of quantum mechanics

    CERN Document Server

    Vaguine, Victor

    2012-01-01

    Since its foundation more than eight decades ago, quantum mechanics has been plagued by enigmas, mysteries and paradoxes and held hostage by quantum positivism. This fact strongly suggests that something is fundamentally wrong with the quantum mechanics paradigm. The best scientific minds, such as Albert Einstein, Louis de Broglie, David Bohm, Richard Feynman and others have spent years of their professional lives attempting to find resolution to the quantum mechanics predicament, with not much success. A shift of the quantum mechanics paradigm toward a deeper physics theory is long overdue.

  14. Mechanical spectral shift reactor

    International Nuclear Information System (INIS)

    Wilson, J.F.; Sherwood, D.G.

    1982-01-01

    A mechanical spectral shift reactor comprises a reactive core having fuel assemblies accommodating both water displacer elements and neutron absorbing control rods for selectively changing the volume of water-moderator in the core. The fuel assemblies with displacer and control rods are arranged in alternating fashion so that one displacer element drive mechanism may move displacer elements in more than one fuel assembly without interfering with the movement of control rods of a corresponding control rod drive mechanisms. (author)

  15. On complexified mechanics and coquaternions

    International Nuclear Information System (INIS)

    Brody, Dorje C; Graefe, Eva-Maria

    2011-01-01

    While real Hamiltonian mechanics and Hermitian quantum mechanics can both be cast in the framework of complex canonical equations, their complex generalizations have hitherto remained tangential. In this communication, quaternionic and coquaternionic (split-signature analogue of quaternions) extensions of Hamiltonian mechanics are introduced and are shown to offer a unifying framework for complexified classical and quantum mechanics. In particular, quantum theories characterized by complex Hamiltonians invariant under spacetime reflection are shown to be equivalent to certain coquaternionic extensions of Hermitian quantum theories. One of the interesting consequences is that the spacetime dimension of these systems is six, not four, on account of the structures of coquaternionic quantum mechanics. (fast track communication)

  16. 6th International Conference on Mechanism Science

    CERN Document Server

    Flores, Paulo

    2017-01-01

    This book collects the most recent advances in mechanism science and machine theory with application to engineering. It contains selected peer-reviewed papers of the sixth International Conference on Mechanism Science, held in Nantes, France, 20-23 September 2016, covering topics on mechanism design and synthesis, mechanics of robots, mechanism analysis, parallel manipulators, tensegrity mechanisms, cable mechanisms, control issues in mechanical systems, history of mechanisms, mechanisms for biomechanics and surgery and industrial and nonindustrial applications.

  17. Mechanism of charity activity

    Directory of Open Access Journals (Sweden)

    Roman B. Golovkin

    2015-12-01

    Full Text Available Objective to establish the essential properties of the mechanism of charitable activities and to formulate the concept of quotmechanism of charitable activityquot. Methods the objective of the study is achieved using the complex of methods which are based on the interaction of dialectical and metaphysical analysis the epistemological properties of which allowed to reveal various aspects of the charitable activities mechanism functioning taking into account the principles of comprehensiveness complexity specificity and objectivity of the research. Results the rules are stated of using the term quotmechanismquot to characterize actions of state and law the essence of the charity mechanism is defined the definition of quotthe mechanism of charitable activity quot is formulated. Scientific novelty for the first time at theoretical level in legal science the definition of quotthe mechanism of charitable activityquot is formulated and its essential properties are set. Practical significance the research will contribute to improving the legal regulation in the field of philanthropy as well as to improving the efficiency and quality of charitable activity in the Russian Federation. nbsp

  18. Advanced mechanics of solids

    CERN Document Server

    Bruhns, Otto T

    2003-01-01

    Mechanics, and in particular, the mechanics of solids, forms the basis of all engi­ neering sciences. It provides the essential foundations for understanding the action of forces on bodies, and the effects of these forces on the straining of the body on the one hand, and on the deformation and motion of the body on the other. Thus, it provides the solutions of many problems with which the would-be engineer is going to be confronted with on a daily basis. In addition, in engineering studies, mechanics has a more vital importance, which many students appreciate only much later. Because of its clear, and analyt­ ical setup, it aids the student to a great extent in acquiring the necessary degree of abstraction ability, and logical thinking, skills without which no engineer in the practice today would succeed. Many graduates have confirmed to me that learning mechanics is generally per­ ceived as difficult. On the other hand, they always also declared that the preoccu­ pation with mechanics made an essential c...

  19. Three-space from quantum mechanics

    International Nuclear Information System (INIS)

    Chew, G.F.; Stapp, H.P.

    1988-01-01

    We formulate a discrete quantum-mechanical precursor to spacetime geometry. The objective is to provide the foundation for a quantum mechanics that is rooted exclusively in quantum-mechanical concepts, with all classical features, including the three-dimensional spatial continuum, emerging dynamically

  20. 44th Aerospace Mechanisms Symposium

    Science.gov (United States)

    Boesiger, Edward A. (Compiler)

    2018-01-01

    The Aerospace Mechanisms Symposium (AMS) provides a unique forum for those active in the design, production and use of aerospace mechanisms. A major focus is the reporting of problems and solutions associated with the development and flight certification of new mechanisms.

  1. Time-dependent mobility and recombination of the photoinduced charge carriers in conjugated polymer/fullerene bulk heterojunction solar cells

    Science.gov (United States)

    Mozer, A. J.; Dennler, G.; Sariciftci, N. S.; Westerling, M.; Pivrikas, A.; Österbacka, R.; Juška, G.

    2005-07-01

    Time-dependent mobility and recombination in the blend of poly[2-methoxy-5-(3,7-dimethyloctyloxy)-phenylene vinylene] (MDMO-PPV) and 1-(3-methoxycarbonyl)propyl-1-phenyl-(6,6)- C61 (PCBM) is studied simultaneously using the photoinduced charge carrier extraction by linearly increasing voltage technique. The charge carriers are photogenerated by a strongly absorbed, 3 ns laser flash, and extracted by the application of a reverse bias voltage pulse after an adjustable delay time (tdel) . It is found that the mobility of the extracted charge carriers decreases with increasing delay time, especially shortly after photoexcitation. The time-dependent mobility μ(t) is attributed to the energy relaxation of the charge carriers towards the tail states of the density of states distribution. A model based on a dispersive bimolecular recombination is formulated, which properly describes the concentration decay of the extracted charge carriers at all measured temperatures and concentrations. The calculated bimolecular recombination coefficient β(t) is also found to be time-dependent exhibiting a power law dependence as β(t)=β0t-(1-γ) with increasing slope (1-γ) with decreasing temperatures. The temperature dependence study reveals that both the mobility and recombination of the photogenerated charge carriers are thermally activated processes with activation energy in the range of 0.1 eV. Finally, the direct comparison of μ(t) and β(t) shows that the recombination of the long-lived charge carriers is controlled by diffusion.

  2. Biexponential photon antibunching: recombination kinetics within the Förster-cycle in DMSO.

    Science.gov (United States)

    Vester, Michael; Grueter, Andreas; Finkler, Björn; Becker, Robert; Jung, Gregor

    2016-04-21

    Time-resolved experiments with pulsed-laser excitation are the standard approach to map the dynamic evolution of excited states, but ground-state kinetics remain hidden or require pump-dump-probe schemes. Here, we exploit the so-called photon antibunching, a purely quantum-optical effect related to single molecule detection to assess the rate constants for a chemical reaction in the electronic ground state. The measurement of the second-order correlation function g((2)), i.e. the evaluation of inter-photon arrival times, is applied to the reprotonation in a Förster-cycle. We find that the antibunching of three different photoacids in the aprotic solvent DMSO significantly differs from the behavior in water. The longer decay constant of the biexponential antibunching tl is linked to the bimolecular reprotonation kinetics of the fully separated ion-pair, independent of the acidic additives. The value of the corresponding bimolecular rate constant, kp = 4 × 10(9) M(-1) s(-1), indicates diffusion-controlled reprotonation. The analysis of tl also allows for the extraction of the separation yield of proton and the conjugated base after excitation and amounts to approximately 15%. The shorter time component ts is connected to the decay of the solvent-separated ion pair. The associated time constant for geminate reprotonation is approximately 3 ± 1 ns in agreement with independent tcspc experiments. These experiments verify that the transfer of quantum-optical experiments to problems in chemistry enables mechanistic conclusions which are hardly accessible by other methods.

  3. Quantification of the free volume in Zr45.0Cu39.3Al7.0Ag8.7 bulk metallic glasses subjected to plastic deformation by calorimetric and dilatometric measurements

    International Nuclear Information System (INIS)

    Zhang Yue; Hahn, Horst

    2009-01-01

    Zr 45.0 Cu 39.3 Al 7.0 Ag 8.7 bulk metallic glasses (BMGs) were prepared using suction casting technique. Plastic deformations were carried out by cold rolling and high-pressure torsion (HPT). The absolute contents of free volume in the as-cast, preheated and deformed samples were determined by differential scanning calorimetry (DSC) and dilatometry using the free volume model (FVM). The parameters required in the FVM are experimentally determined to be b = 0.107, β = 642.1 kJ/mol, D * = 10.3 and T 0 = 496.9 K, respectively. The equilibrium free volume determined by these parameters is in good agreement with that calculated from previous enthalpy relaxation experiments, showing the reliability of the values of the parameters. It is found that the content of free volume in the as-cast sample is 0.533% with respect to the atomic volume of the BMG. The free volume in the HPT deformed sample is determined to be 0.672%, which is the largest among all the samples. The excess free volume introduced by cold rolling is found to increase with the deformation strain and show weak strain rate dependent behavior. Finally, attempts are made to simulate the experimental DSC curve using a bimolecular kinetics in the flow defect model. However, the result shows that the kinetics of free volume may be more complicated than as described as a bimolecular process.

  4. Molecular mechanisms in compatibility and mechanical properties of Polyacrylamide/Polyvinyl alcohol blends.

    Science.gov (United States)

    Wei, Qinghua; Wang, Yanen; Che, Yu; Yang, Mingming; Li, Xinpei; Zhang, Yingfeng

    2017-01-01

    The objectives of this study were to develop a computational model based on molecular dynamics technique to investigate the compatibility and mechanical properties of Polyacrylamide (PAM)/Polyvinyl alcohol (PVA) blends. Five simulation models of PAM/PVA with different composition ratios (4/0, 3/1, 2/2, 1/3, 0/4) were constructed and simulated by using molecular dynamics (MD) simulation. The interaction mechanisms of molecular chains in PAM/PVA blend system were elaborated from the aspects of the compatibility, mechanical properties, binding energy and pair correlation function, respectively. The computed values of solubility parameters for PAM and PVA indicate PAM has a good miscibility with PVA. The results of the static mechanical analysis, based on the equilibrium structures of blends with differing component ratios, shows us that the elastic coefficient, engineering modulus, and ductility are increased with the addition of PVA content, which is 4/0 PAM/PVAPVAPVAPVAPVA. Moreover, binding energy results indicate that a stronger interaction exists among PVA molecular chains comparing with PAM molecular chains, which is why the mechanical properties of blend system increasing with the addition of PVA content. Finally, the results of pair correlation functions (PCFs) between polar functional groups and its surrounding hydrogen atoms, indicated they interact with each other mainly by hydrogen bonds, and the strength of three types of polar functional groups has the order of O(-OH)>O(-C=O)>N(-NH 2 ). This further elaborates the root reason why the mechanical properties of blend system increase with the addition of PVA content. Copyright © 2016 Elsevier Ltd. All rights reserved.

  5. Lectures on statistical mechanics

    CERN Document Server

    Bowler, M G

    1982-01-01

    Anyone dissatisfied with the almost ritual dullness of many 'standard' texts in statistical mechanics will be grateful for the lucid explanation and generally reassuring tone. Aimed at securing firm foundations for equilibrium statistical mechanics, topics of great subtlety are presented transparently and enthusiastically. Very little mathematical preparation is required beyond elementary calculus and prerequisites in physics are limited to some elementary classical thermodynamics. Suitable as a basis for a first course in statistical mechanics, the book is an ideal supplement to more convent

  6. Testing Nonassociative Quantum Mechanics.

    Science.gov (United States)

    Bojowald, Martin; Brahma, Suddhasattwa; Büyükçam, Umut

    2015-11-27

    The familiar concepts of state vectors and operators in quantum mechanics rely on associative products of observables. However, these notions do not apply to some exotic systems such as magnetic monopoles, which have long been known to lead to nonassociative algebras. Their quantum physics has remained obscure. This Letter presents the first derivation of potentially testable physical results in nonassociative quantum mechanics, based on effective potentials. They imply new effects which cannot be mimicked in usual quantum mechanics with standard magnetic fields.

  7. Quantum mechanics in chemistry

    CERN Document Server

    Schatz, George C

    2002-01-01

    Intended for graduate and advanced undergraduate students, this text explores quantum mechanical techniques from the viewpoint of chemistry and materials science. Dynamics, symmetry, and formalism are emphasized. An initial review of basic concepts from introductory quantum mechanics is followed by chapters examining symmetry, rotations, and angular momentum addition. Chapter 4 introduces the basic formalism of time-dependent quantum mechanics, emphasizing time-dependent perturbation theory and Fermi's golden rule. Chapter 5 sees this formalism applied to the interaction of radiation and matt

  8. Statistical mechanics of nonequilibrium liquids

    CERN Document Server

    Evans, Denis J; Craig, D P; McWeeny, R

    1990-01-01

    Statistical Mechanics of Nonequilibrium Liquids deals with theoretical rheology. The book discusses nonlinear response of systems and outlines the statistical mechanical theory. In discussing the framework of nonequilibrium statistical mechanics, the book explains the derivation of a nonequilibrium analogue of the Gibbsian basis for equilibrium statistical mechanics. The book reviews the linear irreversible thermodynamics, the Liouville equation, and the Irving-Kirkwood procedure. The text then explains the Green-Kubo relations used in linear transport coefficients, the linear response theory,

  9. Enhancing Microstructure and Mechanical Properties of AZ31-MWCNT Nanocomposites through Mechanical Alloying

    Directory of Open Access Journals (Sweden)

    J. Jayakumar

    2013-01-01

    Full Text Available Multiwall carbon nanotubes (MWCNTs reinforced Mg alloy AZ31 nanocomposites were fabricated by mechanical alloying and powder metallurgy technique. The reinforcement material MWCNTs were blended in three weight fractions (0.33%, 0.66%, and 1% with the matrix material AZ31 (Al-3%, zinc-1% rest Mg and blended through mechanical alloying using a high energy planetary ball mill. Specimens of monolithic AZ31 and AZ31-MWCNT composites were fabricated through powder metallurgy technique. The microstructure, density, hardness, porosity, ductility, and tensile properties of monolithic AZ31 and AZ31-MWCNT nano composites were characterized and compared. The characterization reveals significant reduction in CNT (carbon nanoTube agglomeration and enhancement in microstructure and mechanical properties due to mechanical alloying through ball milling.

  10. Response of mechanical properties of glasses to their chemical, thermal and mechanical histories

    DEFF Research Database (Denmark)

    Yue, Yuanzheng

    , surface, thermal history or excess entropy of the final glass state. Here I review recent progresses in understanding of the responses of mechanical properties of oxide glasses to the compositional variation, thermal history and mechanical deformation. The tensile strength, elastic modulus and hardness...... of glass fibers are dependent on the thermal history (measured as fictive temperature), tension, chemical composition and redox state. However, the fictive temperature affects the hardness of bulk glass in a complicated manner, i.e., the effect does not exhibit a clear regularity in the range...... and micro-cracks occurring during indentation of a glass is discussed briefly. Finally I describe the future perspectives and challenges in understanding responses of mechanical properties of oxide glasses to compositional variation, thermal history and mechanical deformation....

  11. STRUCTURE OF ECONOMIC MECHANISM

    Directory of Open Access Journals (Sweden)

    L. I. Podderegina

    2006-01-01

    Full Text Available The paper considers and analyzes scientific approaches of economists to the essence and contents of the economic mechanism. Proposals for methodological formation of economic mechanism structure are substantiated in the paper.

  12. Mechanisms for supernova explosions

    International Nuclear Information System (INIS)

    Epstein, R.I.

    1977-01-01

    This report discusses some of the recent developments in the study of one supernova mechanism, the neutrino transport mechanism, and indicates what future developments are needed before this model can be adequately understood. (Auth.)

  13. Mechanical Biological Treatment

    DEFF Research Database (Denmark)

    Bilitewski, B-; Oros, Christiane; Christensen, Thomas Højlund

    2011-01-01

    The basic processes and technologies of composting and anaerobic digestion, as described in the previous chapters, are usually used for specific or source-separated organic waste flows. However, in the 1990s mechanical biological waste treatment technologies (MBT) were developed for unsorted...... or residual waste (after some recyclables removed at the source). The concept was originally to reduce the amount of waste going to landfill, but MBT technologies are today also seen as plants recovering fuel as well as material fractions. As the name suggests the technology combines mechanical treatment...... technologies (screens, sieves, magnets, etc.) with biological technologies (composting, anaerobic digestion). Two main technologies are available: Mechanical biological pretreatment (MBP), which first removes an RDF fraction and then biologically treats the remaining waste before most of it is landfilled...

  14. Mechanical CPR: Who? When? How?

    Science.gov (United States)

    Poole, Kurtis; Couper, Keith; Smyth, Michael A; Yeung, Joyce; Perkins, Gavin D

    2018-05-29

    In cardiac arrest, high quality cardiopulmonary resuscitation (CPR) is a key determinant of patient survival. However, delivery of effective chest compressions is often inconsistent, subject to fatigue and practically challenging.Mechanical CPR devices provide an automated way to deliver high-quality CPR. However, large randomised controlled trials of the routine use of mechanical devices in the out-of-hospital setting have found no evidence of improved patient outcome in patients treated with mechanical CPR, compared with manual CPR. The limited data on use during in-hospital cardiac arrest provides preliminary data supporting use of mechanical devices, but this needs to be robustly tested in randomised controlled trials.In situations where high-quality manual chest compressions cannot be safely delivered, the use of a mechanical device may be a reasonable clinical approach. Examples of such situations include ambulance transportation, primary percutaneous coronary intervention, as a bridge to extracorporeal CPR and to facilitate uncontrolled organ donation after circulatory death.The precise time point during a cardiac arrest at which to deploy a mechanical device is uncertain, particularly in patients presenting in a shockable rhythm. The deployment process requires interruptions in chest compression, which may be harmful if the pause is prolonged. It is recommended that use of mechanical devices should occur only in systems where quality assurance mechanisms are in place to monitor and manage pauses associated with deployment.In summary, mechanical CPR devices may provide a useful adjunct to standard treatment in specific situations, but current evidence does not support their routine use.

  15. Continuum mechanics of anisotropic materials

    CERN Document Server

    Cowin, Stephen C

    2013-01-01

    Continuum Mechanics of Anisotropic Materials(CMAM) presents an entirely new and unique development of material anisotropy in the context of an appropriate selection and organization of continuum mechanics topics. These features will distinguish this continuum mechanics book from other books on this subject. Textbooks on continuum mechanics are widely employed in engineering education, however, none of them deal specifically with anisotropy in materials. For the audience of Biomedical, Chemical and Civil Engineering students, these materials will be dealt with more frequently and greater accuracy in their analysis will be desired. Continuum Mechanics of Anisotropic Materials' author has been a leader in the field of developing new approaches for the understanding of anisotropic materials.

  16. The formation mechanism of mechanically alloyed Fe-20 at% Al powder

    Energy Technology Data Exchange (ETDEWEB)

    Hadef, F., E-mail: hadef77@yahoo.fr [Laboratoire de Recherche sur la Physico-Chimie des Surfaces et Interfaces, LRPCSI, Universite 20 Aout 1955, BP 26, Route d' El-Hadaiek, Skikda 21000 (Algeria); Otmani, A. [Laboratoire de Recherche sur la Physico-Chimie des Surfaces et Interfaces, LRPCSI, Universite 20 Aout 1955, BP 26, Route d' El-Hadaiek, Skikda 21000 (Algeria); Djekoun, A. [Laboratoire de Magnetisme et Spectroscopie des Solides, LM2S, Universite Badji Mokhtar, BP 12 Annaba 23000 (Algeria); Greneche, J.M. [LUNAM, Universite du Maine, Institut des Molecules et Materiaux du Mans, UMR CNRS 6283, 72085 Le Mans (France)

    2013-01-15

    The formation mechanism of the mechanically alloyed Fe-20 at% Al, from elemental Fe and Al powders, has been investigated. The experimental results indicate the formation of a nanocrystalline bcc {alpha}-Fe(Al) solid solution with a lattice parameter close to a{sub {alpha}-Fe(Al)}=0.2890 nm, where each Fe atom is surrounded by (6Fe+2Al) in the first coordination sphere. The reaction mechanism of MA process seems to be controlled by a diffusion phenomenon. Aluminum particles undergo an important refinement to the nanometer scale and then they stick on Fe particles of large sizes. A large number of clear Al/Fe interface areas were generated. The short diffusion path and the presence of high concentration of defects accelerated the solid state reaction. - Highlights: Black-Right-Pointing-Pointer A nanocrystalline bcc {alpha}-Fe(Al) solid solution is formed from elemental Fe and Al powders. Black-Right-Pointing-Pointer The reaction mechanism of MA process seems to be controlled by a diffusion phenomenon. Black-Right-Pointing-Pointer Each Fe atom is surrounded by (6Fe+2Al) in the first coordination sphere.

  17. Mechanism of the superior mechanical strength of nanometer-sized metal single crystals revealed

    KAUST Repository

    Afify, N. D.; Salem, H. G.; Yavari, A.; El Sayed, Tamer S.

    2013-01-01

    Clear understanding of the superior mechanical strength of nanometer-sized metal single crystals is required to derive advanced mechanical components retaining such superiority. Although high quality studies have been reported on nano

  18. MECHANISM TO DRAW MACLAURIN TRISECTRIX

    Directory of Open Access Journals (Sweden)

    Mirela CHERCIU

    2013-05-01

    Full Text Available It is used a geometrical method for generating Maclaurin trisectrix and based on it , thesynthesis of a mechanism that can draw it, is made. The structure of the found mechanism is R-RTRTtype, having two driving elements with correlated movements. This mechanism is analysedand the desired curve is obtained just for certain dimensions of the mechanism. The mechanism’smovement is studied based on some diagrams and different outputs are obtained for certain initialdimensions of the mechanism’s.

  19. Conceptual foundations of quantum mechanics

    International Nuclear Information System (INIS)

    Shimony, A.

    1989-01-01

    Radical innovation in the quantum mechanical framework such as objective indefiniteness, objective chance, objective probability, potentiality, entanglement and quantum nonlocality are discussed and related to the standard formalism. Examples are given which though problematic in classical mechanics are simply explained with these new concepts. Evidence is presented that the conceptual innovations of quantum mechanics cannot be separated from its predictive power. Proposals for solving ''the reduction of the wave packet'' anomaly are presented. Further radical innovations in quantum mechanics are anticipated. (U.K.)

  20. Bohmian mechanics with complex action: A new trajectory-based formulation of quantum mechanics

    International Nuclear Information System (INIS)

    Goldfarb, Yair; Degani, Ilan; Tannor, David J.

    2006-01-01

    In recent years there has been a resurgence of interest in Bohmian mechanics as a numerical tool because of its local dynamics, which suggest the possibility of significant computational advantages for the simulation of large quantum systems. However, closer inspection of the Bohmian formulation reveals that the nonlocality of quantum mechanics has not disappeared--it has simply been swept under the rug into the quantum force. In this paper we present a new formulation of Bohmian mechanics in which the quantum action, S, is taken to be complex. This leads to a single equation for complex S, and ultimately complex x and p but there is a reward for this complexification - a significantly higher degree of localization. The quantum force in the new approach vanishes for Gaussian wave packet dynamics, and its effect on barrier tunneling processes is orders of magnitude lower than that of the classical force. In fact, the current method is shown to be a rigorous extension of generalized Gaussian wave packet dynamics to give exact quantum mechanics. We demonstrate tunneling probabilities that are in virtually perfect agreement with the exact quantum mechanics down to 10 -7 calculated from strictly localized quantum trajectories that do not communicate with their neighbors. The new formulation may have significant implications for fundamental quantum mechanics, ranging from the interpretation of non-locality to measures of quantum complexity