WorldWideScience

Sample records for intramolecular dynamics internal

  1. Intramolecular and nonlinear dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Davis, M.J. [Argonne National Laboratory, IL (United States)

    1993-12-01

    Research in this program focuses on three interconnected areas. The first involves the study of intramolecular dynamics, particularly of highly excited systems. The second area involves the use of nonlinear dynamics as a tool for the study of molecular dynamics and complex kinetics. The third area is the study of the classical/quantum correspondence for highly excited systems, particularly systems exhibiting classical chaos.

  2. Symmetry of quantum intramolecular dynamics

    International Nuclear Information System (INIS)

    Burenin, Alexander V

    2002-01-01

    The paper reviews the current progress in describing quantum intramolecular dynamics using merely symmetry principles as a basis. This closed qualitative approach is of particular interest because it is the only method currently available for a broad class of topical problems in the internal dynamics of molecules. Moreover, a molecule makes a physical system whose collective internal motions are geometrically structured, so that its description by perturbation methods requires a symmetry analysis of this structure. The nature of the geometrical symmetry groups crucial for the closed formulation of the qualitative approach is discussed. In particular, the point group of a molecule is of this type. (methodological notes)

  3. Symmetry of intramolecular quantum dynamics

    CERN Document Server

    Burenin, Alexander V

    2012-01-01

    The main goal of this book is to give a systematic description of intramolecular quantum dynamics on the basis of only the symmetry principles. In this respect, the book has no analogs in the world literature. The obtained models lead to a simple, purely algebraic, scheme of calculation and are rigorous in the sense that their correctness is limited only to the correct choice of symmetry of the internal dynamics. The book is basically intended for scientists working in the field of molecular spectroscopy, quantum and structural chemistry.

  4. Molecular structures and intramolecular dynamics of pentahalides

    Science.gov (United States)

    Ischenko, A. A.

    2017-03-01

    This paper reviews advances of modern gas electron diffraction (GED) method combined with high-resolution spectroscopy and quantum chemical calculations in studies of the impact of intramolecular dynamics in free molecules of pentahalides. Some recently developed approaches to the electron diffraction data interpretation, based on direct incorporation of the adiabatic potential energy surface parameters to the diffraction intensity are described. In this way, complementary data of different experimental and computational methods can be directly combined for solving problems of the molecular structure and its dynamics. The possibility to evaluate some important parameters of the adiabatic potential energy surface - barriers to pseudorotation and saddle point of intermediate configuration from diffraction intensities in solving the inverse GED problem is demonstrated on several examples. With increasing accuracy of the electron diffraction intensities and the development of the theoretical background of electron scattering and data interpretation, it has become possible to investigate complex nuclear dynamics in fluxional systems by the GED method. Results of other research groups are also included in the discussion.

  5. Photochemical Dynamics of Intramolecular Singlet Fission

    Science.gov (United States)

    Lin, Zhou; Iwasaki, Hikari; Van Voorhis, Troy

    2017-06-01

    Singlet fission (SF) converts a singlet exciton (S_1) into a pair of triplet ones (T_1) via a ``multi-exciton'' (ME) intermediate: S_1 \\longleftrightarrow ^1ME \\longleftrightarrow ^1(T_1T_1) \\longrightarrow 2T_1. In exothermic cases, e.g., crystalline pentacene or its derivatives, the quantum yield of SF can reach 200%. With SF doubling the electric current generated by an incident high-energy photon, the solar conversion efficiency in pentacene-based organic photovoltaics (OPVs) can exceed the Shockley-Queisser limit of 33.7%. The ME state is popularly considered to be a dimeric state with significant charge transfer (CT) character that is strongly coupled to both S_1 and ^1(T_1T_1), while this local model lacks strong support from full quantum dynamics studies. Intramolecular SF (ISF) occurring to covalently-bound dimers in the solution phase is an excellent model for a straightforward dynamics simulation of local excitons. In the present study, we investigate the ISF mechanisms for three covalently-bound dimers of pentacene derivatives, including ortho-, meta-, and para-bis(6,13-bis(triisopropylsilylethynyl)pentacene)benzene, in non-protic solvents. Specifically, we propagate the real-time, non-adiabatic quantum mechanical/molecular mechanical (QM/MM) dynamics on the potential energy surfaces associated with the states of S_1, ^1(T_1T_1) and CT. We explore how the energies of these ISF-relevant states and the non-adiabatic couplings between each other fluctuate with time and the instantaneous molecular configuration (e.g., intermonomer distance and orientation). We also quantitatively compare Condon and non-Condon ISF dynamics with solution-phase spectroscopic data. Our results allow us to understand the roles of CT energy levels in the ISF mechanism and propose a design strategy to maximize ISF efficiency. M. B. Smith and J. Michl, Chem. Rev. 110, 6891 (2010). W. Shockley and H. J. Queisser, J. Appl. Phys. 32, 510 (1961). T. C. Berkelbach, M. S. Hybertsen

  6. Dynamics of the excited state intramolecular charge transfer

    International Nuclear Information System (INIS)

    Joo, T.; Kim, C.H.

    2006-01-01

    two log-normal functions, each corresponding to the fluorescence from the LE state and ICT state. Relative populations and the average frequency of the ICT state are shown in Fig.2 and Fig.3, which represents the ICT dynamics and the subsequent solvation process, respectively. The TRF spectra illustrate unambiguously how the ICT and the solvation processes take place for laurdan dissolved in ethanol. First of all, the ICT and the solvation occur in serial. Second, the ICT proceeds in several time scales exhibiting heterogeneity of the molecular conformation in liquid. About one third of the laurdan molecules undergoes ICT immediately in much less than <50 fs time scale. Rest of them undergoes ICT by two time constants, 6.4 ps and 28 ps. The ICT state then undergoes solvation process by 47 ps time constants. Because the molecule is large and flexible, fast inertial component was not observed. In conclusion, TRF spectra in femtosecond resolution reveal detailed intramolecular charge transfer process of laurdan. The ICT process shows a series of time scales due to the conformational heterogeneity in solution. (authors)

  7. Numerical simulation of dynamic quenching of dual-split fluorescence of molecules with intramolecular hydrogen bonds

    International Nuclear Information System (INIS)

    Morozov, V.A.; Chuvulkin, N.D.; Smolenskij, E.A.; Dubina, Yu.M.

    2014-01-01

    The dynamic quenching of intensity pulses of the dual-split fluorescence (DSF) has been simulated using numerical solutions of the equations for the population matrix of five states of the model fluorescent molecule (FM). The state with the highest energy is considered as resonantly excited by irradiation, and two other excited states populated by subsequent relaxation processes are taken as initial states for the FM transitions with emission of the DSF photons. The FM model parameters are selected to fit typical parameters of the molecules with intramolecular proton photo transfer. Quenching is considered as a consequence of non-radiative decay of the FM excited states due to collisions with the quencher molecules. Examples of two types of the DSF quenching of the FM are given. The first type leads to an intramolecular radiationless decay of particular excited states of the FM, and the second one results in radiationless transitions from the same states to the quencher molecule states. (authors)

  8. Molecular Dynamics Simulation of Barnase: Contribution of Noncovalent Intramolecular Interaction to Thermostability

    Directory of Open Access Journals (Sweden)

    Zhiguo Chen

    2013-01-01

    Full Text Available Bacillus amyloliquefaciens ribonuclease Barnase (RNase Ba is a 12 kD (kilodalton small extracellular ribonuclease. It has broad application prospects in agriculture, clinical medicine, pharmaceutical, and so forth. In this work, the thermal stability of Barnase has been studied using molecular dynamics simulation at different temperatures. The present study focuses on the contribution of noncovalent intramolecular interaction to protein stability and how they affect the thermal stability of the enzyme. Profiles of root mean square deviation and root mean square fluctuation identify thermostable and thermosensitive regions of Barnase. Analyses of trajectories in terms of secondary structure content, intramolecular hydrogen bonds and salt bridge interactions indicate distinct differences in different temperature simulations. In the simulations, Four three-member salt bridge networks (Asp8-Arg110-Asp12, Arg83-Asp75-Arg87, Lys66-Asp93-Arg69, and Asp54-Lys27-Glu73 have been identified as critical salt bridges for thermostability which are maintained stably at higher temperature enhancing stability of three hydrophobic cores. The study may help enlighten our knowledge of protein structural properties, noncovalent interactions which can stabilize secondary peptide structures or promote folding, and also help understand their actions better. Such an understanding is required for designing efficient enzymes with characteristics for particular applications at desired working temperatures.

  9. Discovery of intramolecular signal transduction network based on a new protein dynamics model of energy dissipation.

    Directory of Open Access Journals (Sweden)

    Cheng-Wei Ma

    Full Text Available A novel approach to reveal intramolecular signal transduction network is proposed in this work. To this end, a new algorithm of network construction is developed, which is based on a new protein dynamics model of energy dissipation. A key feature of this approach is that direction information is specified after inferring protein residue-residue interaction network involved in the process of signal transduction. This enables fundamental analysis of the regulation hierarchy and identification of regulation hubs of the signaling network. A well-studied allosteric enzyme, E. coli aspartokinase III, is used as a model system to demonstrate the new method. Comparison with experimental results shows that the new approach is able to predict all the sites that have been experimentally proved to desensitize allosteric regulation of the enzyme. In addition, the signal transduction network shows a clear preference for specific structural regions, secondary structural types and residue conservation. Occurrence of super-hubs in the network indicates that allosteric regulation tends to gather residues with high connection ability to collectively facilitate the signaling process. Furthermore, a new parameter of propagation coefficient is defined to determine the propagation capability of residues within a signal transduction network. In conclusion, the new approach is useful for fundamental understanding of the process of intramolecular signal transduction and thus has significant impact on rational design of novel allosteric proteins.

  10. Lipid Regulated Intramolecular Conformational Dynamics of SNARE-Protein Ykt6

    Science.gov (United States)

    Dai, Yawei; Seeger, Markus; Weng, Jingwei; Song, Song; Wang, Wenning; Tan, Yan-Wen

    2016-08-01

    Cellular informational and metabolic processes are propagated with specific membrane fusions governed by soluble N-ethylmaleimide sensitive factor attachment protein receptors (SNARE). SNARE protein Ykt6 is highly expressed in brain neurons and plays a critical role in the membrane-trafficking process. Studies suggested that Ykt6 undergoes a conformational change at the interface between its longin domain and the SNARE core. In this work, we study the conformational state distributions and dynamics of rat Ykt6 by means of single-molecule Förster Resonance Energy Transfer (smFRET) and Fluorescence Cross-Correlation Spectroscopy (FCCS). We observed that intramolecular conformational dynamics between longin domain and SNARE core occurred at the timescale ~200 μs. Furthermore, this dynamics can be regulated and even eliminated by the presence of lipid dodecylphoshpocholine (DPC). Our molecular dynamic (MD) simulations have shown that, the SNARE core exhibits a flexible structure while the longin domain retains relatively stable in apo state. Combining single molecule experiments and theoretical MD simulations, we are the first to provide a quantitative dynamics of Ykt6 and explain the functional conformational change from a qualitative point of view.

  11. Molecular dynamics simulations of single siloxane dendrimers: Molecular structure and intramolecular mobility of terminal groups

    Science.gov (United States)

    Kurbatov, A. O.; Balabaev, N. K.; Mazo, M. A.; Kramarenko, E. Yu.

    2018-01-01

    Molecular dynamics simulations of two types of isolated siloxane dendrimers of various generations (from the 2nd to the 8th) have been performed for temperatures ranging from 150 K to 600 K. The first type of dendrimer molecules has short spacers consisting of a single oxygen atom. In the dendrimers of the second type, spacers are longer and comprised of two oxygen atoms separated by a single silicon atom. A comparative analysis of molecular macroscopic parameters such as the gyration radius and the shape factor as well as atom distributions within dendrimer interior has been performed for varying generation number, temperature, and spacer length. It has been found that the short-spacer dendrimers of the 7th and 8th generations have a stressed central part with elongated bonds and deformed valence angles. Investigation of the time evolution of radial displacements of the terminal Si atoms has shown that a fraction of the Si groups have a reduced mobility. Therefore, rather long time trajectories (of the order of tens of nanoseconds) are required to study dendrimer intramolecular dynamics.

  12. Chromophore-Dependent Intramolecular Exciton-Vibrational Coupling in the FMO Complex: Quantification and Importance for Exciton Dynamics.

    Science.gov (United States)

    Padula, Daniele; Lee, Myeong H; Claridge, Kirsten; Troisi, Alessandro

    2017-11-02

    In this paper, we adopt an approach suitable for monitoring the time evolution of the intramolecular contribution to the spectral density of a set of identical chromophores embedded in their respective environments. We apply the proposed method to the Fenna-Matthews-Olson (FMO) complex, with the objective to quantify the differences among site-dependent spectral densities and the impact of such differences on the exciton dynamics of the system. Our approach takes advantage of the vertical gradient approximation to reduce the computational demands of the normal modes analysis. We show that the region of the spectral density that is believed to strongly influence the exciton dynamics changes significantly in the timescale of tens of nanoseconds. We then studied the impact of the intramolecular vibrations on the exciton dynamics by considering a model of FMO in a vibronic basis and neglecting the interaction with the environment to isolate the role of the intramolecular exciton-vibration coupling. In agreement with the assumptions in the literature, we demonstrate that high frequency modes at energy much larger than the excitonic energy splitting have negligible influence on exciton dynamics despite the large exciton-vibration coupling. We also find that the impact of including the site-dependent spectral densities on exciton dynamics is not very significant, indicating that it may be acceptable to apply the same spectral density on all sites. However, care needs to be taken for the description of the exciton-vibrational coupling in the low frequency part of intramolecular modes because exciton dynamics is more susceptible to low frequency modes despite their small Huang-Rhys factors.

  13. Heat conduction in chain polymer liquids: molecular dynamics study on the contributions of inter- and intramolecular energy transfer.

    Science.gov (United States)

    Ohara, Taku; Yuan, Tan Chia; Torii, Daichi; Kikugawa, Gota; Kosugi, Naohiro

    2011-07-21

    In this paper, the molecular mechanisms which determine the thermal conductivity of long chain polymer liquids are discussed, based on the results observed in molecular dynamics simulations. Linear n-alkanes, which are typical polymer molecules, were chosen as the target of our studies. Non-equilibrium molecular dynamics simulations of bulk liquid n-alkanes under a constant temperature gradient were performed. Saturated liquids of n-alkanes with six different chain lengths were examined at the same reduced temperature (0.7T(c)), and the contributions of inter- and intramolecular energy transfer to heat conduction flux, which were identified as components of heat flux by the authors' previous study [J. Chem. Phys. 128, 044504 (2008)], were observed. The present study compared n-alkane liquids with various molecular lengths at the same reduced temperature and corresponding saturated densities, and found that the contribution of intramolecular energy transfer to the total heat flux, relative to that of intermolecular energy transfer, increased with the molecular length. The study revealed that in long chain polymer liquids, thermal energy is mainly transferred in the space along the stiff intramolecular bonds. This finding implies a connection between anisotropic thermal conductivity and the orientation of molecules in various organized structures with long polymer molecules aligned in a certain direction, which includes confined polymer liquids and self-organized structures such as membranes of amphiphilic molecules in water.

  14. QTAIM and Stress Tensor Characterization of Intramolecular Interactions Along Dynamics Trajectories of a Light-Driven Rotary Molecular Motor.

    Science.gov (United States)

    Wang, Lingling; Huan, Guo; Momen, Roya; Azizi, Alireza; Xu, Tianlv; Kirk, Steven R; Filatov, Michael; Jenkins, Samantha

    2017-06-29

    A quantum theory of atoms in molecules (QTAIM) and stress tensor analysis was applied to analyze intramolecular interactions influencing the photoisomerization dynamics of a light-driven rotary molecular motor. For selected nonadiabatic molecular dynamics trajectories characterized by markedly different S 1 state lifetimes, the electron densities were obtained using the ensemble density functional theory method. The analysis revealed that torsional motion of the molecular motor blades from the Franck-Condon point to the S 1 energy minimum and the S 1 /S 0 conical intersection is controlled by two factors: greater numbers of intramolecular bonds before the hop-time and unusually strongly coupled bonds between the atoms of the rotor and the stator blades. This results in the effective stalling of the progress along the torsional path for an extended period of time. This finding suggests a possibility of chemical tuning of the speed of photoisomerization of molecular motors and related molecular switches by reshaping their molecular backbones to decrease or increase the degree of coupling and numbers of intramolecular bond critical points as revealed by the QTAIM/stress tensor analysis of the electron density. Additionally, the stress tensor scalar and vector analysis was found to provide new methods to follow the trajectories, and from this, new insight was gained into the behavior of the S 1 state in the vicinity of the conical intersection.

  15. Relaxation dynamics in quantum dissipative systems: The microscopic effect of intramolecular vibrational energy redistribution

    Energy Technology Data Exchange (ETDEWEB)

    Uranga-Piña, L. [Facultad de Física, Universidad de la Habana, San Lázaro y L, Vedado, 10400 Havana (Cuba); Institute for Chemistry and Biochemistry, Freie Universität Berlin, Takustr. 3, D-14195 Berlin (Germany); Tremblay, J. C., E-mail: jean.c.tremblay@gmail.com [Institute for Chemistry and Biochemistry, Freie Universität Berlin, Takustr. 3, D-14195 Berlin (Germany)

    2014-08-21

    We investigate the effect of inter-mode coupling on the vibrational relaxation dynamics of molecules in weak dissipative environments. The simulations are performed within the reduced density matrix formalism in the Markovian regime, assuming a Lindblad form for the system-bath interaction. The prototypical two-dimensional model system representing two CO molecules approaching a Cu(100) surface is adapted from an ab initio potential, while the diatom-diatom vibrational coupling strength is systematically varied. In the weak system-bath coupling limit and at low temperatures, only first order non-adiabatic uni-modal coupling terms contribute to surface-mediated vibrational relaxation. Since dissipative dynamics is non-unitary, the choice of representation will affect the evolution of the reduced density matrix. Two alternative representations for computing the relaxation rates and the associated operators are thus compared: the fully coupled spectral basis, and a factorizable ansatz. The former is well-established and serves as a benchmark for the solution of Liouville-von Neumann equation. In the latter, a contracted grid basis of potential-optimized discrete variable representation is tailored to incorporate most of the inter-mode coupling, while the Lindblad operators are represented as tensor products of one-dimensional operators, for consistency. This procedure results in a marked reduction of the grid size and in a much more advantageous scaling of the computational cost with respect to the increase of the dimensionality of the system. The factorizable method is found to provide an accurate description of the dissipative quantum dynamics of the model system, specifically of the time evolution of the state populations and of the probability density distribution of the molecular wave packet. The influence of intra-molecular vibrational energy redistribution appears to be properly taken into account by the new model on the whole range of coupling strengths. It

  16. Dynamics of excited-state intramolecular proton transfer reactions in piroxicam. Role of triplet states

    Science.gov (United States)

    Cho, Dae Won; Kim, Yong Hee; Yoon, Minjoong; Jeoung, Sae Chae; Kim, Dongho

    1994-08-01

    The picosecond time-resolved fluorescence and transient absorption behavior of piroxicam at room temperature are reported. The keto tautomer in the excited singlet state ( 1K*) formed via the fast intramolecular proton transfer (≈ 20 ps) is observed. The short-lived (7.5 ns) triplet state of keto tauomer ( 3K*) is generated from 1K * in toluene whereas it is hardly observed in ethanol. Consequently, rapid reverse proton transfer takes place from 3K * to the enol triplet state ( 3E *.

  17. Detection of Intramolecular Charge Transfer and Dynamic Solvation in Eosin B by Femtosecond Two-Dimensional Electronic Spectroscopy

    Science.gov (United States)

    Ghosh, Soumen; Roscioli, Jerome D.; Beck, Warren F.

    2014-06-01

    We have employed 2D electronic photon echo spectroscopy to study intramolecular charge-transfer dynamics in eosin B. After preparation of the first excited singlet state (S_1) with 40-fs excitation pulses at 520 nm, the nitro group (--NO_2) in eosin B undergoes excited state torsional motion towards a twisted intramolecular charge transfer (TICT) state. As the viscosity of the surrounding solvent increases, the charge-transfer rate decreases because the twisting of the --NO_2 group is hindered. These conclusions are supported by the time evolution of the 2D spectrum, which provides a direct measure of the the ground-to-excited-state energy gap time-correlation function, M(t). In comparison to the inertial and diffusive solvation time scales exhibited by eosin Y, which lacks the nitro group, the M(t) function for eosin B exhibits under the same conditions an additional component on the 150-fs timescale that arises from quenching of the S_1 state by crossing to the TICT state. These results indicate that 2D electronic spectroscopy can be used as a sensitive probe of the rate of charge transfer in a molecular system and of the coupling to the motions of the surrounding solvent. (Supported by grant DE-SC0010847 from the Department of Energy, Office of Basic Energy Sciences, Photosynthetic Systems program.)

  18. Dynamic international oil markets

    International Nuclear Information System (INIS)

    van der Linde, C.

    1992-01-01

    Dynamic International Oil Market Developments and Structure 1860-1990 discusses the logic of changing market structures of the international oil industry. The market structures have, in the course of time, oscillated between competition and oligopoly, as the oil market expanded, matured, stagnated, and expanded again. This book provides a dynamic interpretation of the intensifying struggle among producer, and consumer governments, and oil companies, over the distribution of economic rents and profits. In particular, it shows the shifting fortunes of the governments and companies as they try to control the recurring capacity constraints between the upstream and downstream sectors, generated by the instability of the oil market. The first part of the book examines market conditions and developments between 1860 and 1990; the second part analyzes market structures after 1945

  19. Photoinduced Ultrafast Intramolecular Excited-State Energy Transfer in the Silylene-Bridged Biphenyl and Stilbene (SBS) System: A Nonadiabatic Dynamics Point of View.

    Science.gov (United States)

    Wang, Jun; Huang, Jing; Du, Likai; Lan, Zhenggang

    2015-07-09

    The photoinduced intramolecular excited-state energy-transfer (EET) process in conjugated polymers has received a great deal of research interest because of its important role in the light harvesting and energy transport of organic photovoltaic materials in photoelectric devices. In this work, the silylene-bridged biphenyl and stilbene (SBS) system was chosen as a simplified model system to obtain physical insight into the photoinduced intramolecular energy transfer between the different building units of the SBS copolymer. In the SBS system, the vinylbiphenyl and vinylstilbene moieties serve as the donor (D) unit and the acceptor (A) unit, respectively. The ultrafast excited-state dynamics of the SBS system was investigated from the point of view of nonadiabatic dynamics with the surface-hopping method at the TDDFT level. The first two excited states (S1 and S2) are characterized by local excitations at the acceptor (vinylstilbene) and donor (vinylbiphenyl) units, respectively. Ultrafast S2-S1 decay is responsible for the intramolecular D-A excitonic energy transfer. The geometric distortion of the D moiety play an essential role in this EET process, whereas the A moiety remains unchanged during the nonadiabatic dynamics simulation. The present work provides a direct dynamical approach to understand the ultrafast intramolecular energy-transfer dynamics in SBS copolymers and other similar organic photovoltaic copolymers.

  20. Combining short- and long-range fluorescence reporters with simulations to explore the intramolecular dynamics of an intrinsically disordered protein

    Science.gov (United States)

    Zosel, Franziska; Haenni, Dominik; Soranno, Andrea; Nettels, Daniel; Schuler, Benjamin

    2017-10-01

    Intrinsically disordered proteins (IDPs) are increasingly recognized as a class of molecules that can exert essential biological functions even in the absence of a well-defined three-dimensional structure. Understanding the conformational distributions and dynamics of these highly flexible proteins is thus essential for explaining the molecular mechanisms underlying their function. Single-molecule fluorescence spectroscopy in combination with Förster resonance energy transfer (FRET) is a powerful tool for probing intramolecular distances and the rapid long-range distance dynamics in IDPs. To complement the information from FRET, we combine it with photoinduced electron transfer (PET) quenching to monitor local loop-closure kinetics at the same time and in the same molecule. Here we employed this combination to investigate the intrinsically disordered N-terminal domain of HIV-1 integrase. The results show that both long-range dynamics and loop closure kinetics on the sub-microsecond time scale can be obtained reliably from a single set of measurements by the analysis with a comprehensive model of the underlying photon statistics including both FRET and PET. A more detailed molecular interpretation of the results is enabled by direct comparison with a recent extensive atomistic molecular dynamics simulation of integrase. The simulations are in good agreement with experiment and can explain the deviation from simple models of chain dynamics by the formation of persistent local secondary structure. The results illustrate the power of a close combination of single-molecule spectroscopy and simulations for advancing our understanding of the dynamics and detailed mechanisms in unfolded and intrinsically disordered proteins.

  1. Intramolecular three-colour single pair FRET of intrinsically disordered proteins with increased dynamic range.

    Science.gov (United States)

    Milles, Sigrid; Koehler, Christine; Gambin, Yann; Deniz, Ashok A; Lemke, Edward A

    2012-10-01

    Single molecule observation of fluorescence resonance energy transfer can be used to provide insight into the structure and dynamics of proteins. Using a straightforward triple-colour labelling strategy, we present a measurement and analysis scheme that can simultaneously study multiple regions within single intrinsically disordered proteins.

  2. Intramolecular dynamics within the N-Cap-SH3-SH2 regulatory unit of the c-Abl tyrosine kinase reveal targeting to the cellular membrane.

    Science.gov (United States)

    de Oliveira, Guilherme A P; Pereira, Elen G; Ferretti, Giulia D S; Valente, Ana Paula; Cordeiro, Yraima; Silva, Jerson L

    2013-09-27

    c-Abl is a key regulator of cell signaling and is under strict control via intramolecular interactions. In this study, we address changes in the intramolecular dynamics coupling within the c-Abl regulatory unit by presenting its N-terminal segment (N-Cap) with an alternative function in the cell as c-Abl becomes activated. Using small angle x-ray scattering, nuclear magnetic resonance, and confocal microscopy, we demonstrate that the N-Cap and the Src homology (SH) 3 domain acquire μs-ms motions upon N-Cap association with the SH2-L domain, revealing a stabilizing synergy between these segments. The N-Cap-myristoyl tether likely triggers the protein to anchor to the membrane because of these flip-flop dynamics, which occur in the μs-ms time range. This segment not only presents the myristate during c-Abl inhibition but may also trigger protein localization inside the cell in a functional and stability-dependent mechanism that is lost in Bcr-Abl(+) cells, which underlie chronic myeloid leukemia. This loss of intramolecular dynamics and binding to the cellular membrane is a potential therapeutic target.

  3. Investigation of intramolecular dynamics and conformations of α-, β- and γ-synuclein.

    Directory of Open Access Journals (Sweden)

    Vanessa C Ducas

    Full Text Available The synucleins are a family of natively unstructured proteins consisting of α-, β-, and γ-synuclein which are primarily expressed in neurons. They have been linked to a wide variety of pathologies, including neurological disorders, such as Parkinson's disease (α-synuclein and dementia with Lewy bodies (α- and β-synuclein, as well as various types of cancers (γ-synuclein. Self-association is a key pathological feature of many of these disorders, with α-synuclein having the highest propensity to form aggregates, while β-synuclein is the least prone. Here, we used a combination of fluorescence correlation spectroscopy and single molecule Förster resonance energy transfer to compare the intrinsic dynamics of different regions of all three synuclein proteins to investigate any correlation with putative functional or dysfunctional interactions. Despite a relatively high degree of sequence homology, we find that individual regions sample a broad range of diffusion coefficients, differing by almost a factor of four. At low pH, a condition that accelerates aggregation of α-synuclein, on average smaller diffusion coefficients are measured, supporting a hypothesis that slower intrachain dynamics may be correlated with self-association. Moreover, there is a surprising inverse correlation between dynamics and bulkiness of the segments. Aside from this observation, we could not discern any clear relationship between the physico-chemical properties of the constructs and their intrinsic dynamics. This work suggests that while protein dynamics may play a role in modulating self-association or interactions with other binding partners, other factors, particularly the local cellular environment, may be more important.

  4. Exploring the role of internal friction in the dynamics of unfolded proteins using simple polymer models

    Science.gov (United States)

    Cheng, Ryan R.; Hawk, Alexander T.; Makarov, Dmitrii E.

    2013-02-01

    Recent experiments showed that the reconfiguration dynamics of unfolded proteins are often adequately described by simple polymer models. In particular, the Rouse model with internal friction (RIF) captures internal friction effects as observed in single-molecule fluorescence correlation spectroscopy (FCS) studies of a number of proteins. Here we use RIF, and its non-free draining analog, Zimm model with internal friction, to explore the effect of internal friction on the rate with which intramolecular contacts can be formed within the unfolded chain. Unlike the reconfiguration times inferred from FCS experiments, which depend linearly on the solvent viscosity, the first passage times to form intramolecular contacts are shown to display a more complex viscosity dependence. We further describe scaling relationships obeyed by contact formation times in the limits of high and low internal friction. Our findings provide experimentally testable predictions that can serve as a framework for the analysis of future studies of contact formation in proteins.

  5. Ultrafast intramolecular relaxation dynamics of Mg- and Zn-bacteriochlorophyll a

    Energy Technology Data Exchange (ETDEWEB)

    Kosumi, Daisuke [Osaka City University Advanced Research Institute for Natural Science and Technology, 3-3-138 Sugimoto, Sumiyoshi-ku, Osaka 558-8585 (Japan); CREST/JST, 4-1-8 Honcho, Kawaguchi, Saitama 332-0012 (Japan); Nakagawa, Katsunori; Sakai, Shunsuke [Graduate School of Engineering, Nagoya Institute of Technology, Gokiso-cho, Showa-ku, Nagoya 466-8555 (Japan); Nagaoka, Yuya; Maruta, Satoshi; Sugisaki, Mitsuru [CREST/JST, 4-1-8 Honcho, Kawaguchi, Saitama 332-0012 (Japan); Department of Physics, Graduate School of Science, Osaka City University, 3-3-138 Sugimoto, Sumiyoshi-ku, Osaka 558-8585 (Japan); Dewa, Takehisa [Graduate School of Engineering, Nagoya Institute of Technology, Gokiso-cho, Showa-ku, Nagoya 466-8555 (Japan); PRESTO/JST, 4-1-8 Honcho, Kawaguchi, Saitama 332-0012 (Japan); Nango, Mamoru [The Osaka City University Advanced Research Institute for Natural Science and Technology, 3-3-138 Sugimoto, Sumiyoshi-ku, Osaka 558-8585 (Japan); CREST/JST, 4-1-8 Honcho, Kawaguchi, Saitama 332-0012 (Japan); Graduate School of Engineering, Nagoya Institute of Technology, Gokiso-cho, Showa-ku, Nagoya 466-8555 (Japan); Hashimoto, Hideki [The Osaka City University Advanced Research Institute for Natural Science and Technology, 3-3-138 Sugimoto, Sumiyoshi-ku, Osaka 558-8585 (Japan); CREST/JST, 4-1-8 Honcho, Kawaguchi, Saitama 332-0012 (Japan); Department of Physics, Graduate School of Science, Osaka City University, 3-3-138 Sugimoto, Sumiyoshi-ku, Osaka 558-8585 (Japan)

    2013-07-21

    Ultrafast excited-state dynamics of the photosynthetic pigment (Mg-)bacteriochlorophyll a and its Zn-substituted form were investigated by steady-state absorption/fluorescence and femtosecond pump-probe spectroscopic measurements. The obtained steady-state absorption and fluorescence spectra of bacteriochlorophyll a in solution showed that the central metal compound significantly affects the energy of the Q{sub x} state, but has almost no effect on the Q{sub y} state. Photo-induced absorption spectra were recorded upon excitation of Mg- and Zn-bacteriochlorophyll a into either their Q{sub x} or Q{sub y} state. By comparing the kinetic traces of transient absorption, ground-state beaching, and stimulated emission after excitation to the Q{sub x} or Q{sub y} state, we showed that the Q{sub x} state was substantially incorporated in the ultrafast excited-state dynamics of bacteriochlorophyll a. Based on these observations, the lifetime of the Q{sub x} state was determined to be 50 and 70 fs for Mg- and Zn-bacteriochlorophyll a, respectively, indicating that the lifetime was influenced by the central metal atom due to the change of the energy gap between the Q{sub x} and Q{sub y} states.

  6. Intramolecular interactions stabilizing compact conformations of the intrinsically disordered kinase-inhibitor domain of Sic1: a molecular dynamics investigation.

    Directory of Open Access Journals (Sweden)

    Matteo eLambrughi

    2012-11-01

    Full Text Available Cyclin-dependent kinase inhibitors (CKIs are key regulatory proteins of the eukaryotic cell cycle, which modulate cyclin-dependent kinase (Cdk activity. CKIs perform their inhibitory effect by the formation of ternary complexes with a target kinase and its cognate cyclin. These regulators generally belong to the class of intrinsically disordered proteins (IDPs, which lack a well-defined and organized three-dimensional structure in their free state, undergoing folding upon binding to specific partners. Unbound IDPs are not merely random-coil structures, but can present intrinsically folded structural units (IFSUs and collapsed conformations. These structural features can be relevant to protein function in vivo.The yeast CKI Sic1 is a 284-amino acid IDP that binds to Cdk1 in complex with the Clb5,6 cyclins, preventing phosphorylation of G1 substrates and, therefore, entrance to the S phase. Sic1 degradation, triggered by multiple phosphorylation events, promotes cell-cycle progression. Previous experimental studies pointed out a propensity of Sic1 and its isolated domains to populate both extended and compact conformations. The present contribution provides models of the compact conformations of the Sic1 kinase-inhibitory domain (KID by all-atom molecular-dynamics simulations in explicit solvent and in the absence of interactors. The results are integrated by spectroscopic and spectrometric data. Helical IFSUs are identified, along with networks of intramolecular interactions. The results identify a group of hub residues and electrostatic interactions which are likely to be involved in the stabilization of globular states.

  7. Femtosecond laser studies of ultrafast intramolecular processes

    Energy Technology Data Exchange (ETDEWEB)

    Hayden, C. [Sandia National Laboratories, Livermore, CA (United States)

    1993-12-01

    The goal of this research is to better understand the detailed mechanisms of chemical reactions by observing, directly in time, the dynamics of fundamental chemical processes. In this work femtosecond laser pulses are used to initiate chemical processes and follow the progress of these processes in time. The authors are currently studying ultrafast internal conversion and subsequent intramolecular relaxation in unsaturated hydrocarbons. In addition, the authors are developing nonlinear optical techniques to prepare and monitor the time evolution of specific vibrational motions in ground electronic state molecules.

  8. Phase space bottlenecks: A comparison of quantum and classical intramolecular dynamics for collinear OCS

    International Nuclear Information System (INIS)

    Gibson, L.L.; Schatz, G.C.; Ratner, M.A.; Davis, M.J.

    1987-01-01

    We compare quantum and classical mechanics for a collinear model of OCS at an energy (20 000 cm -1 ) where Davis [J. Chem. Phys. 83, 1016 (1985)] had previously found that phase space bottlenecks associated with golden mean tori inhibit classical flow between different chaotic regions in phase space. Accurate quantum eigenfunctions for this two mode system are found by diagonalizing a large basis of complex Gaussian functions, and these are then used to study the evolution of wave packets which have 20 000 cm -1 average energies. By examining phase space (Husimi) distributions associated with the wave functions, we conclude that these golden mean tori do indeed act as bottlenecks which constrain the wave packets to evolve within one (or a combination of) regions. The golden mean tori do not completely determine the boundaries between regions, however. Bottlenecks associated with resonance trapping and with separatrix formation are also involved. The analysis of the Husimi distributions also indicates that each exact eigenstate is nearly always associated with just one region, and because of this, superpositions of eigenstates that are localized within a region remain localized in that region at all times. This last result differs from the classical picture at this energy where flow across the bottlenecks occurs with a 2--4 ps lifetime. Since the classical phase space area through which flux must pass to cross the bottlenecks is small compared to h for OCS, the observed difference between quantum and classical dynamics is not surprising. Examination of the time development of normal mode energies indicates little or no energy flow quantum mechanically for wave packet initial conditions

  9. Effect of solvent on proton location and dynamic behavior in short intramolecular hydrogen bonds studied by molecular dynamics simulations and NMR experiments

    Energy Technology Data Exchange (ETDEWEB)

    Mori, Yukie, E-mail: mori.yukie@ocha.ac.jp; Masuda, Yuichi

    2015-09-08

    Highlights: • MD simulations were performed to study dynamics of strong hydrogen bonds. • Nuclear magnetic relaxation times of proton were measured in solution. • The hydrogen bond of dibenzoylmethane enol is asymmetric in methanol solution. • Formation or breakage of intermolecular hydrogen bonds can trigger proton transfer. • Dimethylsulfoxide may form a bifurcated hydrogen bond with a hydrogen-bonded system. - Abstract: Hydrogen phthalate anion has a short strong O–H–O hydrogen bond (H-bond). According to previous experimental studies, the H-bond is asymmetric and two tautomers are interconverted in aqueous solutions. In the present study, the effects of polar solvents on the H-bond in a zwitterionic hydrogen phthalate derivative 1 were investigated by quantum mechanics/molecular mechanics molecular dynamics (MD) simulations. The analyses of the trajectories for the methanol solution showed that the H-bonding proton tends to be located closer to the carboxylate group that forms fewer intermolecular H-bonds, than to the other carboxylate group and that the intramolecular proton transfer in 1 is triggered by the breakage and/or formation of an intermolecular H-bond. The enol form of dibenzoylmethane (2) also has a short H-bond, and the OH bond is reported to be rather long (>1.1 Å) in the crystal. In the present study, the effects of the solvent on the H-bond in 2 were investigated by molecular orbital (MO) calculations, MD simulations and nuclear magnetic resonance (NMR) spectroscopy. Density functional theory (DFT) calculations for 2 in vacuum indicated that the barrier height for the intramolecular proton transfer is almost the same as the zero-point energy of the vibrational ground state, resulting in broad distribution of the proton density along the H-bond, owing to the nuclear quantum effect. The OH distances were determined in CCl{sub 4}, acetonitrile, and dimethylsulfoxide solutions from the magnetic dipolar interactions between the {sup 17

  10. Effect of solvent on proton location and dynamic behavior in short intramolecular hydrogen bonds studied by molecular dynamics simulations and NMR experiments

    International Nuclear Information System (INIS)

    Mori, Yukie; Masuda, Yuichi

    2015-01-01

    Highlights: • MD simulations were performed to study dynamics of strong hydrogen bonds. • Nuclear magnetic relaxation times of proton were measured in solution. • The hydrogen bond of dibenzoylmethane enol is asymmetric in methanol solution. • Formation or breakage of intermolecular hydrogen bonds can trigger proton transfer. • Dimethylsulfoxide may form a bifurcated hydrogen bond with a hydrogen-bonded system. - Abstract: Hydrogen phthalate anion has a short strong O–H–O hydrogen bond (H-bond). According to previous experimental studies, the H-bond is asymmetric and two tautomers are interconverted in aqueous solutions. In the present study, the effects of polar solvents on the H-bond in a zwitterionic hydrogen phthalate derivative 1 were investigated by quantum mechanics/molecular mechanics molecular dynamics (MD) simulations. The analyses of the trajectories for the methanol solution showed that the H-bonding proton tends to be located closer to the carboxylate group that forms fewer intermolecular H-bonds, than to the other carboxylate group and that the intramolecular proton transfer in 1 is triggered by the breakage and/or formation of an intermolecular H-bond. The enol form of dibenzoylmethane (2) also has a short H-bond, and the OH bond is reported to be rather long (>1.1 Å) in the crystal. In the present study, the effects of the solvent on the H-bond in 2 were investigated by molecular orbital (MO) calculations, MD simulations and nuclear magnetic resonance (NMR) spectroscopy. Density functional theory (DFT) calculations for 2 in vacuum indicated that the barrier height for the intramolecular proton transfer is almost the same as the zero-point energy of the vibrational ground state, resulting in broad distribution of the proton density along the H-bond, owing to the nuclear quantum effect. The OH distances were determined in CCl 4 , acetonitrile, and dimethylsulfoxide solutions from the magnetic dipolar interactions between the 17 O and 1

  11. Molecular eigenstate spectroscopy: Application to the intramolecular dynamics of some polyatomic molecules in the 3000 to 7000 cm-1 region

    International Nuclear Information System (INIS)

    Perry, D.S.

    1991-05-01

    This project uses high resolution infrared spectroscopy to probe the mechanism of intramolecular vibrational redistribution (IVR) in isolated polyatomic molecules. We have found only vibrationally anharmonic coupling in the C-H stretch region of 1-butyne but rotationally mediated coupling is evident in similar spectra of ethanol. The ''keyhole'' model of IVR was developed to account for the similarities and differences between these molecules. The concepts of the model are being implemented numerically in random matrix calculations. A second F-center laser has been purchased and is now being set up to develop an infrared double resonance technique which can be applied to this problem. 4 refs., 5 figs

  12. Competing Intramolecular vs. Intermolecular Hydrogen Bonds in Solution

    Directory of Open Access Journals (Sweden)

    Peter I. Nagy

    2014-10-01

    Full Text Available A hydrogen bond for a local-minimum-energy structure can be identified according to the definition of the International Union of Pure and Applied Chemistry (IUPAC recommendation 2011 or by finding a special bond critical point on the density map of the structure in the framework of the atoms-in-molecules theory. Nonetheless, a given structural conformation may be simply favored by electrostatic interactions. The present review surveys the in-solution competition of the conformations with intramolecular vs. intermolecular hydrogen bonds for different types of small organic molecules. In their most stable gas-phase structure, an intramolecular hydrogen bond is possible. In a protic solution, the intramolecular hydrogen bond may disrupt in favor of two solute-solvent intermolecular hydrogen bonds. The balance of the increased internal energy and the stabilizing effect of the solute-solvent interactions regulates the new conformer composition in the liquid phase. The review additionally considers the solvent effects on the stability of simple dimeric systems as revealed from molecular dynamics simulations or on the basis of the calculated potential of mean force curves. Finally, studies of the solvent effects on the type of the intermolecular hydrogen bond (neutral or ionic in acid-base complexes have been surveyed.

  13. Sensitivity analysis in molecular dynamics and chemical kinetics and a theory of intramolecular energy transfer in the presence of intense radiation fields

    International Nuclear Information System (INIS)

    Eslava, L.A.

    1983-01-01

    This thesis is an investigation of two topics in the area of molecular and chemical dynamics phenomena. The first topic, Sensitivity Analysis in Molecular Dynamics and Chemical Kinetics, explores the response of the numerical solutions to variation in the input information. After a brief consideration of elementary sensitivity coefficients (i.e. partial derivatives of observables with respect to model parameters), attention is focused on an entire new family of derived coefficients capable of exhibiting important aspects of the underlying dynamics. Each derived sensitivity coefficient has a unique physical interpretation in terms of an experiment or modeling calculation. Also, a fitting model for rotationally inelastic cross sections that accurately predicts cross sections away from the region of parameter space used in the fitting is presented. The global behavior of cross sections in parameter space is examined, and a nonlinear interpolation formula is suggested which utilizes sensitivity information. The second topic, A Theory of Intramolecular Energy Transfer in the Presence of Intense Radiation Fields, represents a theoretical formulation of energy redistribution based on stochastic considerations. The fundamental assumption is that a random phase approximation is valid at specific time intervals. This results in the replacement of the Schrodinger equation by a master-type equation, which is further approximated by a Fokker-Planck diffusion like equation. Energy transfer is described as a flow of probability among the quantum states, and the dissociation of dynamics are embodied in the boundary conditions. By virtue of the continuous character of the Fokker-Planck equation, the computational difficulty of its numerical solution depends only on the number of degrees of freedom and not on the number of states

  14. Intramolecular diffusive motion in alkane monolayers studied by high-resolution quasielastic neutron scattering and molecular dynamics simulations

    DEFF Research Database (Denmark)

    Hansen, Flemming Yssing; Criswell, L.; Fuhrmann, D

    2004-01-01

    Molecular dynamics simulations of a tetracosane (n-C24H50) monolayer adsorbed on a graphite basal-plane surface show that there are diffusive motions associated with the creation and annihilation of gauche defects occurring on a time scale of similar to0.1-4 ns. We present evidence...... that these relatively slow motions are observable by high-energy-resolution quasielastic neutron scattering (QNS) thus demonstrating QNS as a technique, complementary to nuclear magnetic resonance, for studying conformational dynamics on a nanosecond time scale in molecular monolayers....

  15. An intramolecular charge transfer state of carbonyl carotenoids: implications for excited state dynamics of apo-carotenals and retinal

    Czech Academy of Sciences Publication Activity Database

    Polívka, Tomáš; Kaligotla, S.; Chábera, P.; Frank, H.A.

    2011-01-01

    Roč. 13, č. 22 (2011), s. 1463-9076 ISSN 1463-9076 Institutional research plan: CEZ:AV0Z50510513 Keywords : carotenoid * retinal * excited-state dynamics * charge-transfer state Subject RIV: BO - Biophysics Impact factor: 3.573, year: 2011

  16. Photoswitchable Intramolecular H-Stacking of Perylenebisimide

    NARCIS (Netherlands)

    Wang, Jiaobing; Kulago, Artem; Browne, Wesley R.; Feringa, Ben L.

    2010-01-01

    Dynamic control over the formation of H- or J-type aggregates of chromophores is of fundamental importance for developing responsive organic optoelectronic materials. In this study, the first example of photoswitching between a nonstacked and an intramolecularly H-stacked arrangement of

  17. Guidelines for dynamic international programs

    International Nuclear Information System (INIS)

    Gold, M.A.

    1993-01-01

    Matters of global concern-deforestation, global warming, biodiversity loss, sustainable development, fuelwood crises, watershed destruction, and large-scale flooding-frequently involve forests and natural resources. In the future, university students will enter a global setting that more than ever depends on a strong knowledge of international issues. USA land-grant universities are attempting to prepare students for this challenge by improving their international programs including forestry. To improve university programs, several factors will need to be addressed and are discussed, with examples, in this article: commitment of the faculty; program specialization; geographic specialization; reward systems for international contributions; international collaboration; recycled dollars within the university; active teaching programs; research; extention and outreach; language training; international faculty; travel grants; twinning relationships with sister institutions; selective in pursuit of international development assistance; and study centers. 6 refs

  18. Dynamics of International Business Research

    DEFF Research Database (Denmark)

    Kunz, Werner; Manning, Stephan; Pedersen, Torben

    2013-01-01

    This study examines the evolution of the field of international business (IB) research based on a relational cluster analysis of co-citations in the Journal of International Business Studies (JIBS) from 1982 to 2011. Particularly, we examine the changing role of theory in relation to empirical IB...... research. Based on a factor and network analysis, we identify distinct clusters of IB research and their relations over time. We show that the initial focus of IB research on issues of international expansion has shifted towards issues of governance and implementation. In this process, debates on foreign...... entry mode and culture have served as important integrating themes. At the same time, theory debates in IB have expanded from a narrow focus on explaining international expansion, to a rather heterogeneous conglomerate of approaches which have assisted increasingly differentiated empirical research. Our...

  19. New stereoselective intramolecular

    Science.gov (United States)

    Alajarin; Vidal; Tovar; Ramirez De Arellano MC; Cossio; Arrieta; Lecea

    2000-11-03

    Efficient 1,4-asymmetric induction has been achieved in the highly stereocontrolled intramolecular [2 + 2] cycloadditions between ketenimines and imines, leading to 1,2-dihydroazeto[2, 1-b]quinazolines. The chiral methine carbon adjacent to the iminic nitrogen controls the exclusive formation of the cycloadducts with relative trans configuration at C2 and C8. The stepwise mechanistic model, based on theoretical calculations, fully supports the stereochemical outcome of these cycloadditions.

  20. Intramolecular Energy Transfer, Charge Transfer & Hydrogen Bond

    Indian Academy of Sciences (India)

    Ultrafast Dynamics of Chemical Reactions in Condensed Phase: Intramolecular Energy Transfer, Charge Transfer & Hydrogen Bond · PowerPoint Presentation · Slide 3 · Slide 4 · Slide 5 · Slide 6 · Slide 7 · Slide 8 · Slide 9 · Slide 10 · Slide 11 · Slide 12 · Slide 13 · Slide 14 · Slide 15 · Slide 16 · Slide 17 · Slide 18 · Slide 19.

  1. Exploring the Internal Dynamics of Globular Clusters

    Science.gov (United States)

    Watkins, Laura L.; van der Marel, Roeland; Bellini, Andrea; Luetzgendorf, Nora; HSTPROMO Collaboration

    2018-01-01

    Exploring the Internal Dynamics of Globular ClustersThe formation histories and structural properties of globular clusters are imprinted on their internal dynamics. Energy equipartition results in velocity differences for stars of different mass, and leads to mass segregation, which results in different spatial distributions for stars of different mass. Intermediate-mass black holes significantly increase the velocity dispersions at the centres of clusters. By combining accurate measurements of their internal kinematics with state-of-the-art dynamical models, we can characterise both the velocity dispersion and mass profiles of clusters, tease apart the different effects, and understand how clusters may have formed and evolved.Using proper motions from the Hubble Space Telescope Proper Motion (HSTPROMO) Collaboration for a set of 22 Milky Way globular clusters, and our discrete dynamical modelling techniques designed to work with large, high-quality datasets, we are studying a variety of internal cluster properties. We will present the results of theoretical work on simulated clusters that demonstrates the efficacy of our approach, and preliminary results from application to real clusters.

  2. International Conference on Mathematical Fluid Dynamics

    CERN Document Server

    Suzuki, Yukihito

    2016-01-01

    This volume presents original papers ranging from an experimental study on cavitation jets to an up-to-date mathematical analysis of the Navier-Stokes equations for free boundary problems, reflecting topics featured at the International Conference on Mathematical Fluid Dynamics, Present and Future, held 11–14 November 2014 at Waseda University in Tokyo. The contributions address subjects in one- and two-phase fluid flows, including cavitation, liquid crystal flows, plasma flows, and blood flows. Written by internationally respected experts, these papers highlight the connections between mathematical, experimental, and computational fluid dynamics. The book is aimed at a wide readership in mathematics and engineering, including researchers and graduate students interested in mathematical fluid dynamics.

  3. Phenylene ring dynamics in phenoxy and the effect of intramolecular linkages on the dynamics of some engineering thermoplastics below the glass transition temperature

    International Nuclear Information System (INIS)

    Arrese-Igor, Silvia; Arbe, Arantxa; Alegria, Angel; Colmenero, Juan; Frick, Bernhard

    2007-01-01

    We have investigated the dynamics of phenylene rings in the engineering thermoplastic bisphenol-A poly(hydroxyether)--phenoxy--below its glass transition temperature by means of neutron scattering techniques. A relatively wide dynamic range has been covered thanks to the combination of two different types of neutron spectrometers, time of flight and backscattering. Partially deuterated samples have been used in order to isolate the phenylene ring dynamics. The resulting neutron scattering signal of phenoxy has been described by a model that considers π flips and oscillation motions for phenylene rings. The associated time scales are broadly distributed with mean activation energies equal to 0.41 and 0.21 eV, respectively. Finally, a comparative study with the literature shows that the dielectric and mechanical γ relaxation in phenoxy exhibit good correlation with the characteristic times of the aliphatic chain published elsewhere and with the characteristic times observed for the motion of phenylene rings by neutron scattering. These findings are discussed in a more general framework that considers, in addition, previous results on other polymers, which also contain the bisphenol-A unit

  4. IR Dissociation spectroscopy of ethylene bonded to CH4, CH2D2 and CD4 and intramolecular dynamics of NeCl2

    International Nuclear Information System (INIS)

    Janda, K.C.

    1986-01-01

    The goal of my project is to understand how intramolecular vibrational relaxation effects the high resolution spectroscopy of vibrationally excited molecules. Their first results indicated that for molecular complexes of ethylene, vibrationally excited in the nu 7 out-of-plane bending mode, IVR is so fast that high resolution spectroscopy is vitiated by lifetime broadening. Only for rare gas-ethylene complexes was rotational resolution achieved. These results led them to postulate that IVR in ethylene complexes occurs by a V-T,R mechanism where the rate is limited by angular momentum constraints

  5. Lipase-catalyzed asymmetric synthesis of naphtho[2,3-c]furan-1(3H)-one derivatives by a one-pot dynamic kinetic resolution/intramolecular Diels-Alder reaction: Total synthesis of (-)-himbacine.

    Science.gov (United States)

    Sugiyama, Koji; Kawanishi, Shinji; Oki, Yasuhiro; Kamiya, Marin; Hanada, Ryosuke; Egi, Masahiro; Akai, Shuji

    2018-04-01

    One-pot sequential reactions using the acyl moieties installed by enzymatic dynamic kinetic resolution of alcohols have been little investigated. In this work, the acryloyl moiety installed via the lipase/oxovanadium combo-catalyzed dynamic kinetic resolution of a racemic dienol [4-(cyclohex-1-en-1-yl)but-3-en-2-ol or 1-(cyclohex-1-en-1-yl)but-2-en-1-ol] with a (Z)-3-(phenylsulfonyl)acrylate underwent an intramolecular Diels-Alder reaction in a one-pot procedure to produce an optically active naphtho[2,3-c]furan-1(3H)-one derivative (98% ee). This method was successfully applied to the asymmetric total synthesis of (-)-himbacine. Copyright © 2017 Elsevier Ltd. All rights reserved.

  6. International Conference on Dynamic Crack Propagation

    CERN Document Server

    1973-01-01

    The planning meeting for a conference on Dynamic Crack Propagation was held at M.LT. in February 1971 and attended by research workers from several industrial, governmental and academic organizations. It was felt that a more specialized meeting would provide a better opportunity for both U.S. and foreign researchers to exchange their ideas and views on dynamic fracture, a subject which is seldom emphasized in national or international fracture conferences. Dynamic crack propagation has been a concern to specialists in many fields: continuum mechanics, metallurgy, geology, polymer chemistry, orthopedics, applied mathematics, as well as structural design and testing. It impinges on a wide variety of problems such as rock breaking and earthquakes, pressure vessels and line pipes, comminution and the per­ formance of armament and ordnance, etc. Advances have been numerous, covering theories and experiments from both the microscopic and macro­ scopic points of view. Hence, the need for comparing the theoretical ...

  7. International Conference on Applications in Nonlinear Dynamics

    CERN Document Server

    Longhini, Patrick; Palacios, Antonio

    2017-01-01

    This book presents collaborative research works carried out by experimentalists and theorists around the world in the field of nonlinear dynamical systems. It provides a forum for applications of nonlinear systems while solving practical problems in science and engineering. Topics include: Applied Nonlinear Optics, Sensor, Radar & Communication Signal Processing, Nano Devices, Nonlinear Biomedical Applications, Circuits & Systems, Coupled Nonlinear Oscillator, Precision Timing Devices, Networks, and other contemporary topics in the general field of Nonlinear Science. This book provides a comprehensive report of the various research projects presented at the International Conference on Applications in Nonlinear Dynamics (ICAND 2016) held in Denver, Colorado, 2016. It can be a valuable tool for scientists and engineering interested in connecting ideas and methods in nonlinear dynamics with actual design, fabrication and implementation of engineering applications or devices.

  8. Plasma internal inductance dynamics in a tokamak

    International Nuclear Information System (INIS)

    Romero, J.A.

    2010-01-01

    A lumped parameter model for tokamak plasma current and inductance time evolution as a function of plasma resistance, non-inductive current drive sources and boundary voltage or poloidal field coil current drive is presented. The model includes a novel formulation leading to exact equations for internal inductance and plasma current dynamics. Having in mind its application in a tokamak inductive control system, the model is expressed in state space form, the preferred choice for the design of control systems using modern control systems theory. The choice of system states allows many interesting physical quantities such as plasma current, inductance, magnetic energy, and resistive and inductive fluxes be made available as output equations. The model is derived from energy conservation theorem, and flux balance theorems, together with a first order approximation for flux diffusion dynamics. The validity of this approximation has been checked using experimental data from JET showing an excellent agreement.

  9. Molecular eigenstate spectroscopy: Application to the intramolecular dynamics of some polyatomic molecules in the 3000 to 7000 cm{sup {minus}1} region

    Energy Technology Data Exchange (ETDEWEB)

    Perry, D.S. [Univ. of Akron, OH (United States)

    1993-12-01

    Intramolecular vibrational redistribution (IVR) appears to be a universal property of polyatomic molecules in energy regions where the vibrational density of states is greater than about 5 to 30 states per cm{sup {minus}1}. Interest in IVR stems from its central importance to the spectroscopy, photochemistry, and reaction kinetics of these molecules. A bright state, {var_phi}{sub s}, which may be a C-H stretching vibration, carries the oscillator strength from the ground state. This bright state may mix with bath rotational-vibrational levels to form a clump of molecular eigenstates, each of which carries a portion of the oscillator strength from the ground state. In this work the authors explicitly resolve transitions to each of these molecular eigenstates. Detailed information about the nature of IVR is contained in the frequencies and intensities of the observed discrete transitions. The primary goal of this research is to probe the coupling mechanisms by which IVR takes place. The most fundamental distinction to be made is between anharmonic coupling which is independent of molecular rotation and rotationally-mediated coupling. The authors are also interested in the rate at which IVR takes place. Measurements are strictly in the frequency domain but information is obtained about the decay of the zero order state, {var_phi}{sub s}, which could be prepared in a hypothetical experiment as a coherent excitation of the clump of molecular eigenstates. As the coherent superposition dephases, the energy would flow from the initially prepared mode into nearby overtones and combinations of lower frequency vibrational modes. The decay of the initially prepared mode is related to a pure sequence infrared absorption spectrum by a Fourier transform.

  10. A molecular dynamics study of intramolecular proton transfer reaction of malonaldehyde in solution based upon a mixed quantum-classical approximation. II. Proton transfer reaction in non-polar solvent

    Science.gov (United States)

    Kojima, H.; Yamada, A.; Okazaki, S.

    2015-05-01

    The intramolecular proton transfer reaction of malonaldehyde in neon solvent has been investigated by mixed quantum-classical molecular dynamics (QCMD) calculations and fully classical molecular dynamics (FCMD) calculations. Comparing these calculated results with those for malonaldehyde in water reported in Part I [A. Yamada, H. Kojima, and S. Okazaki, J. Chem. Phys. 141, 084509 (2014)], the solvent dependence of the reaction rate, the reaction mechanism involved, and the quantum effect therein have been investigated. With FCMD, the reaction rate in weakly interacting neon is lower than that in strongly interacting water. However, with QCMD, the order of the reaction rates is reversed. To investigate the mechanisms in detail, the reactions were categorized into three mechanisms: tunneling, thermal activation, and barrier vanishing. Then, the quantum and solvent effects were analyzed from the viewpoint of the reaction mechanism focusing on the shape of potential energy curve and its fluctuations. The higher reaction rate that was found for neon in QCMD compared with that found for water solvent arises from the tunneling reactions because of the nearly symmetric double-well shape of the potential curve in neon. The thermal activation and barrier vanishing reactions were also accelerated by the zero-point energy. The number of reactions based on these two mechanisms in water was greater than that in neon in both QCMD and FCMD because these reactions are dominated by the strength of solute-solvent interactions.

  11. Dynamical Properties of Internal Shocks Revisited

    Energy Technology Data Exchange (ETDEWEB)

    Pe’er, Asaf; Long, Killian [Physics Department, University College Cork, Cork (Ireland); Casella, Piergiorgio [INAF, Osservatorio Astronomico di Roma, Via Frascati 33, I-00078 Monteporzio Catone (Italy)

    2017-09-01

    Internal shocks between propagating plasma shells, originally ejected at different times with different velocities, are believed to play a major role in dissipating the kinetic energy, thereby explaining the observed light curves and spectra in a large range of transient objects. Even if initially the colliding plasmas are cold, following the first collision, the plasma shells are substantially heated, implying that in a scenario of multiple collisions, most collisions take place between plasmas of non-zero temperatures. Here, we calculate the dynamical properties of plasmas resulting from a collision between arbitrarily hot plasma shells, moving at arbitrary speeds. We provide simple analytical expressions valid for both ultrarelativistic and Newtonian velocities for both hot and cold plasmas. We derive the minimum criteria required for the formation of the two-shock wave system, and show that in the relativistic limit, the minimum Lorentz factor is proportional to the square root of the ratio of the initial plasmas enthalpies. We provide basic scaling laws of synchrotron emission from both the forward and reverse-shock waves, and show how these can be used to deduce the properties of the colliding shells. Finally, we discuss the implications of these results in the study of several astronomical transients, such as X-ray binaries, radio-loud quasars, and gamma-ray bursts.

  12. 8th International Workshop on Chiral Dynamics

    CERN Document Server

    2016-01-01

    The International Workshop on Chiral Dynamics 2015, the eighth in a series which started in 1994 at MIT, and was later held in Mainz (1997), Jefferson Lab (2000 and 2012), Bonn (2003), Duke (2006) and Bern (2009), will take place in Pisa, from June 29 to July 3 2015, and will be jointly hosted by the Department of Physics of the University of Pisa and the Pisa branch of the Istituto Nazionale di Fisica Nucleare. The purpose of this workshop series is to bring physicists together who are active in this field, as well as those who are interested, to discuss and debate the most recent achievements and future developments. The workshop will have a near equal contribution from theorists and experimentalists and, as in the latest editions, a strong synergy with the lattice community will be present. Topics: Hadron structure Isospin breaking in hadronic systems Meson-meson and meson-baryon interaction Effective field theory and chiral perturbation theory Few-body physics Compton scattering and the polarizabilities o...

  13. Ultrafast internal rotational dynamics of the azido group in (4S)-azidoproline: Chemical exchange 2DIR spectroscopic investigations

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Kyung-Koo; Park, Kwang-Hee; Joo, Cheonik; Kwon, Hyeok-Jun; Han, Hogyu [Department of Chemistry, Korea University, Seoul 136-701 (Korea, Republic of); Ha, Jeong-Hyon [Multidimensional Spectroscopy Laboratory, Korea Basic Science Institute, Seoul 136-713 (Korea, Republic of); Park, Sungnam, E-mail: spark8@korea.ac.kr [Department of Chemistry, Korea University, Seoul 136-701 (Korea, Republic of); Multidimensional Spectroscopy Laboratory, Korea Basic Science Institute, Seoul 136-713 (Korea, Republic of); Cho, Minhaeng, E-mail: mcho@korea.ac.kr [Department of Chemistry, Korea University, Seoul 136-701 (Korea, Republic of); Multidimensional Spectroscopy Laboratory, Korea Basic Science Institute, Seoul 136-713 (Korea, Republic of); Research Institute for Natural Sciences, Korea University, Seoul 136-713 (Korea, Republic of)

    2012-03-02

    Graphical abstract: Internal rotational dynamics of the azido group in SA (Ac-(4S)-Azp-NHMe) was studied in real time by using ultrafast 2DIR spectroscopic method. The time constant of the internal rotation around the C{sup {gamma}}-N{sup {delta}} bond in SA was determined to be {tau}{sub ir} = 5.1 ps, which is found to be much faster than that around the C-C bond in ethane. Highlights: Black-Right-Pointing-Pointer Femtosecond two-dimensional IR spectroscopy of internal rotational dynamics. Black-Right-Pointing-Pointer Stereo-electronic effects of azido group in azido-derivatized proline peptide. Black-Right-Pointing-Pointer The timescale of the azido group internal rotation is about 5.1 ps. - Abstract: The azido group in 4-azidoproline (Azp) derivative, SA (Ac-(4S)-Azp-NHMe), can form an intramolecular electrostatic interaction with the backbone peptide in the s-trans and C{sup {gamma}}-endo conformations of SA. As a result, the azido group exists as two forms, bound and free, which are defined by the presence and absence of such interaction, respectively. The bound and free azido forms are spectrally resolved in the azido IR spectrum of SA in CHCl{sub 3}. Using the two-dimensional infrared (2DIR) and polarization-controlled IR pump-probe methods, we investigated the internal rotational and orientational relaxation dynamics of the azido group and determined the internal rotational time constant of the azido group to be 5.1 ps. The internal rotational motion is found to be responsible for the early part of the orientational relaxation of the azido group in SA. Thus, the femtosecond 2DIR spectroscopy is shown to be an ideal tool for studying ultrafast conformational dynamics of SA.

  14. A dynamic balanced scorecard for identification internal process factor

    Directory of Open Access Journals (Sweden)

    Javad sofiyabadi

    2012-08-01

    Full Text Available We present a dynamic balanced score card (BSC to investigate the strategic internal process management factors. The proposed dynamic BSC emphasizes on internal processes aspect, and using VIKOR and Shannon Entropy, determinants the internal processes, process management and improvement and all important factors are ranked. The current study first introduces dynamic BSC and examines effective factors on the process. The proposed model focuses on internal processes perspective of BSC and determines importance degree of each factor is used using VIKOR decision-making techniques.

  15. Intramolecular Association within the SAFT Framework

    DEFF Research Database (Denmark)

    Avlund, Ane Søgaard; Kontogeorgis, Georgios; Chapman, Walter G.

    2011-01-01

    A general theory for modelling intramolecular association within the SAFT framework is proposed. Sear and Jackson [Phys. Rev. E. 50 (1), 386 (1994)] and Ghonasgi and Chapman [J. Chem. Phys. 102 (6), 2585 (1995)] have previously extended SAFT to include intramolecular association for chains with two...... the contribution to the Helmholtz free energy from association (inter- as well as intramolecularly) at equilibrium. Sear and Jackson rederived the contribution to the Helmholtz free energy from association from the theory by Wertheim [J. Stat. Phys. 42 (3–4), 459 (1986)] with inclusion of intramolecular...

  16. International Conference on Dynamical Systems : Theory and Applications

    CERN Document Server

    2016-01-01

    The book is a collection of contributions devoted to analytical, numerical and experimental techniques of dynamical systems, presented at the international conference "Dynamical Systems: Theory and Applications," held in Lódz, Poland on December 7-10, 2015. The studies give deep insight into new perspectives in analysis, simulation, and optimization of dynamical systems, emphasizing directions for future research. Broadly outlined topics covered include: bifurcation and chaos in dynamical systems, asymptotic methods in nonlinear dynamics, dynamics in life sciences and bioengineering, original numerical methods of vibration analysis, control in dynamical systems, stability of dynamical systems, vibrations of lumped and continuous sytems, non-smooth systems, engineering systems and differential equations, mathematical approaches to dynamical systems, and mechatronics.

  17. International Conference on Dynamical Systems : Theory and Applications

    CERN Document Server

    2016-01-01

    The book is the second volume of a collection of contributions devoted to analytical, numerical and experimental techniques of dynamical systems, presented at the international conference "Dynamical Systems: Theory and Applications," held in Lódz, Poland on December 7-10, 2015. The studies give deep insight into new perspectives in analysis, simulation, and optimization of dynamical systems, emphasizing directions for future research. Broadly outlined topics covered include: bifurcation and chaos in dynamical systems, asymptotic methods in nonlinear dynamics, dynamics in life sciences and bioengineering, original numerical methods of vibration analysis, control in dynamical systems, stability of dynamical systems, vibrations of lumped and continuous sytems, non-smooth systems, engineering systems and differential equations, mathematical approaches to dynamical systems, and mechatronics.

  18. NASA plan for international crustal dynamics studies

    Science.gov (United States)

    1979-01-01

    The international activities being planned as part of the NASA geodynamics program are described. Methods of studying the Earth's crustal movements and deformation characteristics are discussed. The significance of the eventual formalations of earthquake predictions methods is also discussed.

  19. Internal Mass Motion for Spacecraft Dynamics and Control

    National Research Council Canada - National Science Library

    Hall, Christopher D

    2008-01-01

    We present a detailed description of the application of a noncanonical Hamiltonian formulation to the modeling, analysis, and simulation of the dynamics of gyrostat spacecraft with internal mass motion...

  20. 9th IFToMM International Conference on Rotor Dynamics

    CERN Document Server

    2015-01-01

    This book presents the proceedings of the 9th IFToMM International Conference on Rotor Dynamics. This conference is a premier global event that brings together specialists from the university and industry sectors worldwide in order to promote the exchange of knowledge, ideas, and information on the latest developments and applied technologies in the dynamics of rotating machinery. The coverage is wide ranging, including, for example, new ideas and trends in various aspects of bearing technologies, issues in the analysis of blade dynamic behavior,  condition monitoring of different rotating machines, vibration control, electromechanical and fluid-structure interactions in rotating machinery, rotor dynamics of micro, nano, and cryogenic machines, and applications of rotor dynamics in transportation engineering. Since its inception 32 years ago, the IFToMM International Conference on Rotor Dynamics has become an irreplaceable point of reference for those working in the field, and this book reflects the high qua...

  1. XXIII International Conference on Nonlinear Dynamics of Electronic Systems

    CERN Document Server

    Stoop, Ruedi; Stramaglia, Sebastiano

    2017-01-01

    This book collects contributions to the XXIII international conference “Nonlinear dynamics of electronic systems”. Topics range from non-linearity in electronic circuits to synchronisation effects in complex networks to biological systems, neural dynamics and the complex organisation of the brain. Resting on a solid mathematical basis, these investigations address highly interdisciplinary problems in physics, engineering, biology and biochemistry.

  2. Dynamics in international market segmentation of new product growth

    NARCIS (Netherlands)

    Lemmens, A.; Croux, C.; Stremersch, S.

    2012-01-01

    Prior international segmentation studies have been static in that they have identified segments that remain stable over time. This paper shows that country segments in new product growth are intrinsically dynamic. We propose a semiparametric hidden Markov model to dynamically segment countries based

  3. Conserving Coherence and Storing Energy during Internal Conversion: Photoinduced Dynamics of cis- and trans-Azobenzene Radical Cations

    KAUST Repository

    Munkerup, Kristin

    2017-10-24

    Light harvesting via energy storage in azobenzene has been a key topic for decades, and the process of energy distribution over the molecular degrees of freedom following photoexcitation remains to be understood. Dynamics of a photoexcited system can exhibit high degrees of non-ergodicity when it is driven by just a few degrees of freedom. Typically, an internal conversion leads to the loss of such localization of dynamics, as the intramolecular energy becomes statistically redistributed over all molecular degrees of freedom. Here, we present a unique case where the excitation energy remains localized even subsequent to internal conversion. Strong-field ionization is used to prepare cis- and trans-azobenzene radical cations on the D1 surface with little excess energy, at the equilibrium neutral geometry. These D1 ions are preferably formed because in this case D1 and D0 switch place in the presence of the strong laser field. The post-ionization dynamics is dictated by the potential energy landscape. The D1 surface is steep downhill along the cis/trans isomerization coordinate and towards a common minimum shared by the two isomers in the region of D1/D0 conical intersection. Coherent cis/trans torsional motion along this coordinate is manifested in the ion transients by a cosine modulation. In this scenario, D0 becomes populated with molecules that are energized mainly along the cis-trans isomerization coordinate, with the kinetic energy above the cis-trans inter-conversion barrier. These activated azobenzene molecules easily cycle back and forth along the D0 surface, and give rise to several periods of modulated signal before coherence is lost. This persistent localization of the internal energy during internal conversion is provided by the steep downhill potential energy surface, small initial internal energy content, and a strong hole-lone pair interaction that drives the molecule along the cis-trans isomerization coordinate to facilitate the transition between

  4. [Internal migration trends and regional dynamics].

    Science.gov (United States)

    Trabelsi, M

    1992-01-01

    This study concerns aspects of regional development in Tunisia. It specifically considers how economic factors affect income differentials among regions, and ways in which these in turn influence trends in internal migration. The effect of these trends on urbanization is also explored.

  5. Gender and Internal Migration dynamics in Ghana

    African Journals Online (AJOL)

    Agribotix GCS 068

    Internal migration is an inherent part of the processes of development and structural ... to rural-urban migrants by Government policies and strategies to enhance the ... Several studies globally indicate that migration is a driver of growth and an .... More recent approaches of networks theories and transnational approaches to ...

  6. Neutron Imaging Reveals Internal Plant Hydraulic Dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Warren, Jeffrey [ORNL; Bilheux, Hassina Z [ORNL; Kang, Misun [ORNL; Voisin, Sophie [ORNL; Cheng, Chu-Lin [ORNL; Horita, Jusuke [ORNL; Perfect, Edmund [ORNL

    2013-01-01

    Many terrestrial ecosystem processes are constrained by water availability and transport within the soil. Knowledge of plant water fluxes is thus critical for assessing mechanistic processes linked to biogeochemical cycles, yet resolution of root structure and xylem water transport dynamics has been a particularly daunting task for the ecologist. Through neutron imaging, we demonstrate the ability to non-invasively monitor individual root functionality and water fluxes within Zea mays L. (maize) and Panicum virgatum L. (switchgrass) seedlings growing in a sandy medium. Root structure and growth were readily imaged by neutron radiography and neutron computed tomography. Seedlings were irrigated with water or deuterium oxide and imaged through time as a growth lamp was cycled on to alter leaf demand for water. Sub-millimeter scale resolution reveals timing and magnitudes of root water uptake, redistribution within the roots, and root-shoot hydraulic linkages, relationships not well characterized by other techniques.

  7. 4th International Conference on Structural Nonlinear Dynamics and Diagnosis

    CERN Document Server

    2018-01-01

    This book presents contributions on the most active lines of recent advanced research in the field of nonlinear mechanics and physics selected from the 4th International Conference on Structural Nonlinear Dynamics and Diagnosis. It includes fifteen chapters by outstanding scientists, covering various aspects of applications, including road tanker dynamics and stability, simulation of abrasive wear, energy harvesting, modeling and analysis of flexoelectric nanoactuator, periodic Fermi–Pasta–Ulam problems, nonlinear stability in Hamiltonian systems, nonlinear dynamics of rotating composites, nonlinear vibrations of a shallow arch, extreme pulse dynamics in mode-locked lasers, localized structures in a photonic crystal fiber resonator, nonlinear stochastic dynamics, linearization of nonlinear resonances, treatment of a linear delay differential equation, and fractional nonlinear damping. It appeals to a wide range of experts in the field of structural nonlinear dynamics and offers researchers and engineers a...

  8. Excited state Intramolecular Proton Transfer in Anthralin

    DEFF Research Database (Denmark)

    Møller, Søren; Andersen, Kristine B.; Spanget-Larsen, Jens

    1998-01-01

    Quantum chemical calculations performed on anthralin (1,8-dihydroxy-9(10H)-anthracenone) predict the possibility of an excited-state intramolecular proton transfer process. Fluorescence excitation and emission spectra of the compound dissolved in n-hexane at ambient temperature results in an unus......Quantum chemical calculations performed on anthralin (1,8-dihydroxy-9(10H)-anthracenone) predict the possibility of an excited-state intramolecular proton transfer process. Fluorescence excitation and emission spectra of the compound dissolved in n-hexane at ambient temperature results......, associated with an excited-state intramolecular proton transfer process....

  9. Are international fund flows related to exchange rate dynamics?

    NARCIS (Netherlands)

    Li, Suxiao; de Haan, Jakob; Scholtens, Bert

    2018-01-01

    Employing monthly data for 53 countries between 1996 and 2015, we investigate the relationship between international fund flows and exchange rate dynamics. We find strong co-movement between funds flows (as measured with the EPFR Global data base) and bilateral real exchange rates vis-à-vis the USD.

  10. Dynamics of Receptor-Mediated Nanoparticle Internalization into Endothelial Cells

    Science.gov (United States)

    Gonzalez-Rodriguez, David; Barakat, Abdul I.

    2015-01-01

    Nanoparticles offer a promising medical tool for targeted drug delivery, for example to treat inflamed endothelial cells during the development of atherosclerosis. To inform the design of such therapeutic strategies, we develop a computational model of nanoparticle internalization into endothelial cells, where internalization is driven by receptor-ligand binding and limited by the deformation of the cell membrane and cytoplasm. We specifically consider the case of nanoparticles targeted against ICAM-1 receptors, of relevance for treating atherosclerosis. The model computes the kinetics of the internalization process, the dynamics of binding, and the distribution of stresses exerted between the nanoparticle and the cell membrane. The model predicts the existence of an optimal nanoparticle size for fastest internalization, consistent with experimental observations, as well as the role of bond characteristics, local cell mechanical properties, and external forces in the nanoparticle internalization process. PMID:25901833

  11. Symposium of the International Society of Dynamic Games

    CERN Document Server

    Haurie, Alain; Annals of the International Society of Dynamic Games

    1994-01-01

    Recent years have witnessed a surge of activity in the field of dynamic both theory and applications. Theoretical as well as practical games, in problems in zero-sum and nonzero-sum games, continuous time differential and discrete time multistage games, and deterministic and stochastic games games are currently being investigated by researchers in diverse disciplines, such as engineering, mathematics, biology, economics, management science, and political science. This surge of interest has led to the formation of the International Society of Dynamic Games (ISDG) in 1990, whose primary goal is to foster the development of advanced research and applications in the field of game theory. One important activity of the Society is to organize biannually an international symposium which aims at bringing together all those who contribute to the development of this active field of applied science. In 1992 the symposium was organized in Grimentz, Switzerland, under the supervision of an international scientific committe...

  12. Dynamic response of a riser under excitation of internal waves

    Science.gov (United States)

    Lou, Min; Yu, Chenglong; Chen, Peng

    2015-12-01

    In this paper, the dynamic response of a marine riser under excitation of internal waves is studied. With the linear approximation, the governing equation of internal waves is given. Based on the rigid-lid boundary condition assumption, the equation is solved by Thompson-Haskell method. Thus the velocity field of internal waves is obtained by the continuity equation. Combined with the modified Morison formula, using finite element method, the motion equation of riser is solved in time domain with Newmark-β method. The computation programs are compiled to solve the differential equations in time domain. Then we get the numerical results, including riser displacement and transfiguration. It is observed that the internal wave will result in circular shear flow, and the first two modes have a dominant effect on dynamic response of the marine riser. In the high mode, the response diminishes rapidly. In different modes of internal waves, the deformation of riser has different shapes, and the location of maximum displacement shifts. Studies on wave parameters indicate that the wave amplitude plays a considerable role in response displacement of riser, while the wave frequency contributes little. Nevertheless, the internal waves of high wave frequency will lead to a high-frequency oscillation of riser; it possibly gives rise to fatigue crack extension and partial fatigue failure.

  13. Dust devil dynamics in the internal vortex region

    International Nuclear Information System (INIS)

    Onishchenko, O G; Pokhotelov, O A; Horton, W

    2015-01-01

    A hydrodynamic model for dust devil dynamics in the internal vortex region is analyzed. It is shown that the results concerning the growing plumes investigated by Onishchenko et al (2014) for the short time domain can be applied to the study of vortex motion in the internal region for longer times. It is demonstrated that these convective plumes in an atmosphere with weak, large-scale toroidal motion inhomogeneity in the vertical direction can be a subject for further exponential growth over time. (invited comment)

  14. Bifurcation phenomena in internal dynamics of gear systems

    Directory of Open Access Journals (Sweden)

    Hortel M.

    2007-10-01

    Full Text Available The impact effects in gear mesh represent specific phenomena in the dynamic investigation of highspeed light transmission systems with kinematic couplings. They are caused of greater dynamic than static elastic deformations in meshing gear profiles. In term of internal dynamics they are influenced among others by time heteronomous stiffness functions in gear mesh and resonance tuning of stiffness level. The damping in gear mesh and in gear system is concerned significantly in the amplitude progress, greatness and phase shift of relative motion towards stiffness function alternatively towards its modify form in gear mesh. In consequence of these and another actions rise above resonance characteristics certain singular locations with jump amplitude course.

  15. 5th International Conference on Dynamics in Logistics

    CERN Document Server

    Kotzab, Herbert; Pannek, Jürgen

    2017-01-01

    These proceedings contain research papers presented at the 5th International Conference on Dynamics in Logistics, held in Bremen, Germany, February 2016. The conference is concerned with dynamic aspects of logistic processes and networks. The spectrum of topics reaches from modeling, planning and control of processes over supply chain management and maritime logistics to innovative technologies and robotic applications for cyber-physical production and logistic systems. The growing dynamic confronts the area of logistics with completely new challenges: it must become possible to describe, identify and analyze the process changes. Moreover, logistic processes and networks must be redevised to be rapidly and flexibly adaptable to continuously changing conditions. The book primarily addresses researchers and practitioners from the field of industrial engineering and logistics, but it may also be beneficial for graduate students.

  16. 4th International Conference on Dynamics in Logistics

    CERN Document Server

    Pannek, Jürgen; Thoben, Klaus-Dieter

    2016-01-01

    This contributed volume brings together research papers presented at the 4th International Conference on Dynamics in Logistics, held in Bremen, Germany in February 2014. The conference focused on the identification, analysis and description of the dynamics of logistics processes and networks. Topics covered range from the modeling and planning of processes, to innovative methods like autonomous control and knowledge management, to the latest technologies provided by radio frequency identification, mobile communication, and networking. The growing dynamic poses wholly new challenges: logistics processes and networks must be(come) able to rapidly and flexibly adapt to constantly changing conditions. The book primarily addresses the needs of researchers and practitioners from the field of logistics, but will also be beneficial for graduate students.

  17. The potential value of dynamic materials control in international safeguards

    International Nuclear Information System (INIS)

    Keepin, G.R.; Lovett, J.E.

    1979-01-01

    The difficulties inherent in conventional materials accountancy based on semi-annual or annual shutdown cleanout physical inventories have been recognized for many years. The increasing importance of international nuclear materials safeguards, coupled with the availability of advanced non-destructive measurement technology which could be installed on or near process lines, has led to the development of the concept of advanced or dynamic materials control. The potential benefits of dynamic materials control in terms of significantly improved detection capabilities (ranging from a few kilograms of plutonium down to perhaps a few hundred grams, even for large-scale bulk processing facilities), and even more dramatically improved detection timeliness (typically a few days, and potentially only a few hours, in advanced facilities), are reviewed. At least twelve major dynamic material control systems already in existence or in the process of being installed are noted, and some of the essential characteristics are discussed. Some currently unresolved questions are explored, and future prospects for the concept of dynamic material control in international safeguards are reviewed. (author)

  18. Epr, structural characteristics and intramolecular movements of some phenoxyl radicals in toluene

    OpenAIRE

    Nizameev, I.; Pudovkin, M.; Kadirov, M.

    2010-01-01

    The method of electron paramagnetic resonance (EPR) spectroscopy was used for studying magnetic and dynamic properties of phenoxyl radicals in toluene at 170-370 K. Characteristics of intramolecular motion and structure of phenoxyl radicals were determined from the temperature dependence of EPR spectra. For all the given compounds the activation energies of transitions between the conformers were calculated.

  19. Solvent control of intramolecular proton transfer

    DEFF Research Database (Denmark)

    Manolova, Y.; Marciniak, Heinz; Tschierlei, S.

    2017-01-01

    of molecules in the enol and zwitterionic proton transfer (PT) form exists in the ground state. However, the zwitterion is the energetically favored one in the electronically excited state. Optical excitation of the enol form results in intramolecular proton transfer and formation of the PT form within 1.4 ps...

  20. INTRAMOLECULAR ISOTOPE EFFECTS IN HYDROCARBON MASS SPECTRA

    Energy Technology Data Exchange (ETDEWEB)

    Stevenson, D. P.; Schachtschneider, J. H.

    1963-07-15

    Approximate calculations based on the quasi-equilibrium rate theory of the origin of mass spectra are shown to lead to an approximately correct magnitude for the intramolecular ( pi /sup -/) isotope effect on C--H bond dissociation probabilities of various deuterohydrocarbons. (auth)

  1. Fifth International Conference on the Dynamics of Information Systems

    CERN Document Server

    Walteros, Jose; Pardalos, Panos

    2014-01-01

    The contributions of this volume stem from the “Fifth International Conference on the Dynamics of Information Systems” held in Gainesville, FL in February 2013, and discuss state-of the-art  techniques in handling problems and solutions in the broad field of information systems. Dynamics of Information Systems: Computational and Mathematical Challenges presents diverse aspects of modern information systems with an emphasis on interconnected network systems and related topics, such as signal and message reconstruction, network connectivity, stochastic network analysis, cyber and computer security, community and cohesive structures in complex networks. Information systems are a vital part of modern societies. They are essential to our daily actions, including social networking, business and bank transactions, as well as sensor communications. The rapid increase in these capabilities has enabled us with more powerful systems, readily available to sense, control, disperse, and analyze information.

  2. 2nd International Conference on Dynamics of Disasters

    CERN Document Server

    Nagurney, Anna; Pardalos, Panos

    2016-01-01

    This volume results from the “Second International Conference on Dynamics of Disasters” held in Kalamata, Greece, June 29-July 2, 2015. The conference covered particular topics involved in natural and man-made disasters such as war, chemical spills, and wildfires. Papers in this volume examine the finer points of disasters through: · Critical infrastructure protection · Resiliency · Humanitarian logistic · Relief supply chains · Cooperative game theory · Dynamical systems · Decision making under risk and uncertainty · Spread of diseases · Contagion · Funding for disaster relief · Tools for emergency preparedness · Response, and risk mitigation Multi-disciplinary theories, tools, techniques and methodologies are linked with disasters from mitigation and preparedness to response and recovery. The interdisciplinary approach to problems in economics, optimization, government, management, business, humanities, engineering, medicine, mathematics, computer science, behavioral studies, emergency servi...

  3. How internal drainage affects evaporation dynamics from soil surfaces ?

    Science.gov (United States)

    Or, D.; Lehmann, P.; Sommer, M.

    2017-12-01

    Following rainfall, infiltrated water may be redistributed internally to larger depths or lost to the atmosphere by evaporation (and by plant uptake from depths at longer time scales). A large fraction of evaporative losses from terrestrial surfaces occurs during stage1 evaporation during which phase change occurs at the wet surface supplied by capillary flow from the soil. Recent studies have shown existence of a soil-dependent characteristic length below which capillary continuity is disrupted and a drastic shift to slower stage 2 evaporation ensues. Internal drainage hastens this transition and affect evaporative losses. To predict the transition to stage 2 and associated evaporative losses, we developed an analytical solution for evaporation dynamics with concurrent internal drainage. Expectedly, evaporative losses are suppressed when drainage is considered to different degrees depending on soil type and wetness. We observe that high initial water content supports rapid drainage and thus promotes the sheltering of soil water below the evaporation depth. The solution and laboratory experiments confirm nonlinear relationship between initial water content and total evaporative losses. The concept contributes to establishing bounds on regional surface evaporation considering rainfall characteristics and soil types.

  4. Highly efficient induction of chirality in intramolecular

    Science.gov (United States)

    Cossio; Arrieta; Lecea; Alajarin; Vidal; Tovar

    2000-06-16

    Highly stereocontrolled, intramolecular [2 + 2] cycloadditions between ketenimines and imines leading to 1,2-dihydroazeto[2, 1-b]quinazolines have been achieved. The source of stereocontrol is a chiral carbon atom adjacent either to the iminic carbon or nitrogen atom. In the first case, the stereocontrol stems from the preference for the axial conformer in the first transition structure. In the second case, the origin of the stereocontrol lies on the two-electron stabilizing interaction between the C-C bond being formed and the sigma orbital corresponding to the polar C-X bond, X being an electronegative atom. These models can be extended to other related systems for predicting the stereochemical outcome in this intramolecular reaction.

  5. Intramolecular and Transannular Diels-Alder Reactions

    DEFF Research Database (Denmark)

    Tanner, David Ackland; Ascic, Erhad

    2014-01-01

    Few reactions can compete with the Diels-Alder (DA) [4+2] cycloaddition for the rapid and efficient generation of molecular complexity. The DA reaction is atom-economic and stereospecific, as well as diastereo- and regioselective. The intramolecular version (IMDA) of the DA cycloaddition and its...... and dienophile, methods for acceleration of IMDA reactions (such as use of high pressure) and catalysis (using oxophilic or carbophilic metal complexes, Brønsted acids, and enzymes). The use of furans as diene components (IMDAF), intramolecular hetero-DA (IMHDA) and IMDA reactions with inverse electron demand...... are also covered. Applications of IMDA to asymmetric synthesis (from substrate control through to enantioselective catalysis, including organocatalysis) are presented, along with tandem sequences involving IMDA cycloaddition. A theme pervading the whole chapter is the use of IMDA reactions for the total...

  6. [Fluid dynamics of supercritical helium within internally cooled cabled superconductors

    International Nuclear Information System (INIS)

    Van Sciver, S.W.

    1995-01-01

    The Applied Superconductivity Center of the University of Wisconsin-Madison proposes to conduct research on low temperature helium fluid dynamics as it applies to the cooling of internally cooled cabled superconductors (ICCS). Such conductors are used in fusion reactor designs including most of the coils in ITER. The proposed work is primarily experimental involving measurements of transient and steady state pressure drop in a variety of conductor configurations. Both model and prototype conductors for actual magnet designs will be investigated. The primary goal will be to measure and model the friction factor for these complex geometries. In addition, an effort will be made to study transient processes such as heat transfer and fluid expulsion associated with quench conditions

  7. Observing and modeling nonlinear dynamics in an internal combustion engine

    International Nuclear Information System (INIS)

    Daw, C.S.; Kennel, M.B.; Finney, C.E.; Connolly, F.T.

    1998-01-01

    We propose a low-dimensional, physically motivated, nonlinear map as a model for cyclic combustion variation in spark-ignited internal combustion engines. A key feature is the interaction between stochastic, small-scale fluctuations in engine parameters and nonlinear deterministic coupling between successive engine cycles. Residual cylinder gas from each cycle alters the in-cylinder fuel-air ratio and thus the combustion efficiency in succeeding cycles. The model close-quote s simplicity allows rapid simulation of thousands of engine cycles, permitting statistical studies of cyclic-variation patterns and providing physical insight into this technologically important phenomenon. Using symbol statistics to characterize the noisy dynamics, we find good quantitative matches between our model and experimental time-series measurements. copyright 1998 The American Physical Society

  8. International Symposium on Dynamics of Ordering Processes in Condensed Matter

    CERN Document Server

    Furukawa, H

    1988-01-01

    The International Symposium on Dynamics of Ordering Processes in Condensed Matter was held at the Kansai Seminar House, Kyoto, for four days, from 27 to 30 August 1987, under the auspices of the Physical Soci­ ety of Japan. The symposium was financially supported by the four orga­ nizations and 45 companies listed on other pages in this volume. We are very grateful to all of them and particularly to the greatest sponsor, the Commemorative Association for the Japan World Exposition 1970. A total Df 22 invited lectures and 48 poster presentations were given and 110 participants attended from seven nations. An objective of the Symposium was to review and extend our present understanding of the dynamics of ordering processes in condensed matters, (for example, alloys, polymers and fluids), that are brought to an un­ stable state by sudden change of such external parameters as temperature and pressure. A second objective, no less important, was to identify new fields of science that might be investigated by sim...

  9. Ego, drives, and the dynamics of internal objects

    Directory of Open Access Journals (Sweden)

    Simon eBoag

    2014-07-01

    Full Text Available This paper addresses the relationship between the ego, id, and internal objects. While ego psychology views the ego as autonomous of the drives, a less well-known alternative position views the ego as constituted by the drives. Based on Freud’s ego-instinct account, this position has developed into a school of thought which postulates that the drives act as knowers. Given that there are multiple drives, this position proposes that personality is constituted by multiple knowers. Following on from Freud, the ego is viewed as a composite sub-set of the instinctual drives (ego-drives, whereas those drives cut off from expression form the id. The nature of the ‘self’ is developed in terms of identification and the possibility of multiple personalities is also established. This account is then extended to object-relations and the explanatory value of the ego-drive account is discussed in terms of the addressing the nature of ego-structures and the dynamic nature of internal objects. Finally, the impact of psychological conflict and the significance of repression for understanding the nature of splits within the psyche are also discussed.

  10. Intramolecular 13C analysis of tree rings provides multiple plant ecophysiology signals covering decades.

    Science.gov (United States)

    Wieloch, Thomas; Ehlers, Ina; Yu, Jun; Frank, David; Grabner, Michael; Gessler, Arthur; Schleucher, Jürgen

    2018-03-22

    Measurements of carbon isotope contents of plant organic matter provide important information in diverse fields such as plant breeding, ecophysiology, biogeochemistry and paleoclimatology. They are currently based on 13 C/ 12 C ratios of specific, whole metabolites, but we show here that intramolecular ratios provide higher resolution information. In the glucose units of tree-ring cellulose of 12 tree species, we detected large differences in 13 C/ 12 C ratios (>10‰) among carbon atoms, which provide isotopically distinct inputs to major global C pools, including wood and soil organic matter. Thus, considering position-specific differences can improve characterisation of soil-to-atmosphere carbon fluxes and soil metabolism. In a Pinus nigra tree-ring archive formed from 1961 to 1995, we found novel 13 C signals, and show that intramolecular analysis enables more comprehensive and precise signal extraction from tree rings, and thus higher resolution reconstruction of plants' responses to climate change. Moreover, we propose an ecophysiological mechanism for the introduction of a 13 C signal, which links an environmental shift to the triggered metabolic shift and its intramolecular 13 C signature. In conclusion, intramolecular 13 C analyses can provide valuable new information about long-term metabolic dynamics for numerous applications.

  11. On combinatorial properties of elementary intramolecular operations

    Directory of Open Access Journals (Sweden)

    Vladimir Rogojin

    2014-11-01

    Full Text Available Here we tackle a problem from biology in terms of discrete mathematics. We are interested in a complex DNA manipulation process happening in eukaryotic organisms of a subclass of ciliate species called {\\it Stichotrichia} during so-called gene assembly. This process is in particular interesting since one can interpret gene assembly in ciliates as sorting of permutations. We survey here results related to studies on sorting permutations with some specific rewriting rules that formalize elementary intramolecular gene assembly operations. The research question is ``what permutation may be sorted with our operations?"

  12. Total internal reflection and dynamic light scattering microscopy of gels

    Science.gov (United States)

    Gregor, Brian F.

    Two different techniques which apply optical microscopy in novel ways to the study of biological systems and materials were built and applied to several samples. The first is a system for adapting the well-known technique of dynamic light scattering (DLS) to an optical microscope. This can detect and scatter light from very small volumes, as compared to standard DLS which studies light scattering from volumes 1000x larger. The small scattering volume also allows for the observation of nonergodic dynamics in appropriate samples. Porcine gastric mucin (PGM) forms a gel at low pH which lines the epithelial cell layer and acts as a protective barrier against the acidic stomach environment. The dynamics and microscopic viscosity of PGM at different pH levels is studied using polystyrene microspheres as tracer particles. The microscopic viscosity and microrheological properties of the commercial basement membrane Matrigel are also studied with this instrument. Matrigel is frequently used to culture cells and its properties remain poorly determined. Well-characterized and purely synthetic Matrigel substitutes will need to have the correct rheological and morphological characteristics. The second instrument designed and built is a microscope which uses an interferometry technique to achieve an improvement in resolution 2.5x better in one dimension than the Abbe diffraction limit. The technique is based upon the interference of the evanescent field generated on the surface of a prism by a laser in a total internal reflection geometry. The enhanced resolution is demonstrated with fluorescent samples. Additionally. Raman imaging microscopy is demonstrated using the evanescent field in resonant and non-resonant samples, although attempts at applying the enhanced resolution technique to the Raman images were ultimately unsuccessful. Applications of this instrument include high resolution imaging of cell membranes and macroscopic structures in gels and proteins. Finally, a third

  13. Computational fluid dynamics for turbomachinery internal air systems.

    Science.gov (United States)

    Chew, John W; Hills, Nicholas J

    2007-10-15

    Considerable progress in development and application of computational fluid dynamics (CFD) for aeroengine internal flow systems has been made in recent years. CFD is regularly used in industry for assessment of air systems, and the performance of CFD for basic axisymmetric rotor/rotor and stator/rotor disc cavities with radial throughflow is largely understood and documented. Incorporation of three-dimensional geometrical features and calculation of unsteady flows are becoming commonplace. Automation of CFD, coupling with thermal models of the solid components, and extension of CFD models to include both air system and main gas path flows are current areas of development. CFD is also being used as a research tool to investigate a number of flow phenomena that are not yet fully understood. These include buoyancy-affected flows in rotating cavities, rim seal flows and mixed air/oil flows. Large eddy simulation has shown considerable promise for the buoyancy-driven flows and its use for air system flows is expected to expand in the future.

  14. Solar neutrinos, helioseismology and the solar internal dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Turck-Chieze, Sylvaine [Service d' Astrophysique/IRFU/DSM/CEA, 91191 Gif sur Yvette Cedex (France); Couvidat, Sebastien, E-mail: sylvaine.turck-chieze@cea.fr, E-mail: couvidat@stanford.edu [HEPL, Stanford University, Stanford, CA 94305 (United States)

    2011-08-15

    Neutrinos are fundamental particles ubiquitous in the Universe and whose properties remain elusive despite more than 50 years of intense research activity. This review illustrates the importance of solar neutrinos in astrophysics, nuclear physics and particle physics. After a description of the historical context, we remind the reader of the noticeable properties of these particles and of the stakes of the solar neutrino puzzle. The standard solar model triggered persistent efforts in fundamental physics to predict the solar neutrino fluxes, and its constantly evolving predictions have been regularly compared with the detected neutrino signals. Anticipating that this standard model could not reproduce the internal solar dynamics, a seismic solar model was developed which enriched theoretical neutrino flux predictions with in situ observation of acoustic and gravity waves propagating in the Sun. This seismic model contributed to the stabilization of the neutrino flux predictions. This review recalls the main historical steps, from the pioneering Homestake mine experiment and the GALLEX-SAGE experiments capturing the first proton-proton neutrinos. It emphasizes the importance of the SuperKamiokande and SNO detectors. Both experiments demonstrated that the solar-emitted electron neutrinos are partially transformed into other neutrino flavors before reaching the Earth. This sustained experimental effort opens the door to neutrino astronomy, with long-base lines and underground detectors. The success of BOREXINO in detecting the {sup 7}Be neutrino signal alone instills confidence in physicists' ability to detect each neutrino source separately. It justifies the building of a new generation of detectors to measure the entire solar neutrino spectrum in greater detail, as well as supernova neutrinos. A coherent picture has emerged from neutrino physics and helioseismology. Today, new paradigms take shape in these two fields: neutrinos are massive particles, but their

  15. Modeling the dynamics of internal flooding - verification analysis

    International Nuclear Information System (INIS)

    Filipov, K.

    2011-01-01

    The results from conducted software WATERFOW's verification analysis, developed for the purposes of reactor building internal flooding analysis have been presented. For the purpose of benchmarking the integrated code MELCOR is selected. Considering the complex structure of reactor building, the sample tests were used to cover the characteristic points of the internal flooding analysis. The inapplicability of MELCOR to the internal flooding study has been proved

  16. Dynamics of International Reserve Accumulation in Turkish Economy

    Directory of Open Access Journals (Sweden)

    Duygu Ayhan

    2015-05-01

    Full Text Available Many of the emerging market economies embody macroeconomic and structural vulnerabilities due to large deficits, high inflation, slowing growth and heavy reliance on short-term capital inflows. Therefore, accumulation of international reserve holdings has been frequently used by authorities to serve as an insurance against the volatility of the capital flows and strengthen the fragile nature of these economies. Turkish economy, classified as one of the most fragile of the emerging economies, has been experiencing a similar process of international reserve accumulation. The chronically high current account deficit and low savings rate boost the importance of international reserves. Thus, the aim of this paper is to investigate the determinants of international reserves in Turkey. The dataset covers the 2000-2013 period. Consequently, we find that the international reserve accumulation is mainly explained by current account balance, per capita income and past crisis experience.

  17. Stabilization of Rigid Body Dynamics by Internal and External Torques

    National Research Council Canada - National Science Library

    Bloch, A. M; Krishnaprasad, P. S; Marsden, J. E; Sanchez de Alvarez, G

    1990-01-01

    ...] with quadratic feedback torques for internal rotors. We show that with such torques, the equations for the rigid body with momentum wheels are Hamiltonian with respect to a Lie-Poisson bracket structure. Further...

  18. Internal and external dynamics of regional cooperation in Central Asia

    Directory of Open Access Journals (Sweden)

    Mirzokhid Rakhimov

    2010-07-01

    Challenges of the 21-century require a broader partnership and cooperation. Future prospects of multilateral regional and international cooperation in Central Asia will depend on correlations of national, regional and global interests. It is necessary first of all strong dialogs between Central Asian republics itself. Central Asian geopolitical, economic and security challenges are connected and solution could come jointly. Future regional cooperation, strong international partnership would promote more stability, economic reforms and democratization to region and beyond.

  19. International Conference on Structural Nonlinear Dynamics and Diagnosis

    CERN Document Server

    CSNDD 2012; CSNDD 2014

    2015-01-01

    This book, which presents the peer-reviewed post-proceedings of CSNDD 2012 and CSNDD 2014, addresses the important role that relevant concepts and tools from nonlinear and complex dynamics could play in present and future engineering applications. It includes 22 chapters contributed by outstanding researchers and covering various aspects of applications, including: structural health monitoring, diagnosis and damage detection, experimental methodologies, active vibration control and smart structures, passive control of structures using nonlinear energy sinks, vibro-impact dynamic MEMS/NEMS/AFM, energy-harvesting materials and structures, and time-delayed feedback control, as well as aspects of deterministic versus stochastic dynamics and control of nonlinear phenomena in physics.  Researchers and engineers interested in the challenges posed and opportunities offered by nonlinearities in the development of passive and active control strategies, energy harvesting, novel design criteria, modeling and characteriz...

  20. Energy harvesting by dynamic unstability and internal resonance for piezoelectric beam

    Energy Technology Data Exchange (ETDEWEB)

    Lan, Chunbo; Qin, Weiyang, E-mail: 353481781@qq.com; Deng, Wangzheng [Department of Engineering Mechanics, Northwestern Polytechnical University, Xi' an 710072 (China)

    2015-08-31

    We investigated the energy harvesting of a vertical beam with tip mass under vertical excitations. We applied dynamic unstability and internal resonance to improve the efficiency of harvesting. The experiments of harmonic excitation were carried out. Results show that for the beam there exist internal resonances in the dynamically unstable and the buckling bistable cases. The dynamic unstability is a determinant for strong internal resonance or mode coupling, which can be used to create a large output from piezoelectric patches. Then, the experiments of stochastic excitation were carried out. Results prove that the internal resonance or mode coupling can transfer the excitation energy to the low order modes, mainly the first and the second one. This can bring about a large output voltage. For a stochastic excitation, it is proved that there is an optimal weight of tip mass for realizing internal resonance and producing large outputs.

  1. Effects of acid concentration on intramolecular charge transfer ...

    Indian Academy of Sciences (India)

    rate. Time-dependent density functional theory calculations have been performed to understand the observed spectroscopic results. Keywords. Intramolecular charge transfer; absorption and fluorescence; time resolved fluorescence measurements; acid concentration dependence; time-dependent density functional theory.

  2. Intramolecularly Hydrogen-Bonded Polypyrroles as Electro-Optical Sensors

    National Research Council Canada - National Science Library

    Nicholson, Jesse

    2001-01-01

    We have developed a new class of polypyrroles bearing both hydrogen-bond acceptor and hydrogen-donor groups such that the intramolecular hydrogen bonding holds the system planar enhancing conjugation...

  3. Handbook of international insurance between global dynamics and local contingencies

    CERN Document Server

    Venard, Bertrand

    2007-01-01

    THE HANDBOOK OF INTERNATIONAL INSURANCE Gordon Stewart, President, Insurance Information Institute, New York, USA "The globalization of insurance markets means that understanding both international developments and local trends around the world is now fundamental for insurance executives coping with today’s complex and competitive environment. By providing such a comprehensive picture of the world’s insurance markets, this unique and necessary book becomes an essential tool for anyone seeking to operate wisely and successfully. Richard D. Phillips, Professor and Chairman, Department of Risk Management and Insurance, Georgia State University, Atlanta, USA "Comprehensive surveys, written by international experts, provide in depth descriptions and discuss recent developments of the world’s major insurance markets. Each chapter contains essential insights for insurance executives and academic researchers interested in risk management and the globalization of insurance markets." Patrick Liedtke, Secretary Ge...

  4. Internal dynamics of intense twin beams and their coherence

    Czech Academy of Sciences Publication Activity Database

    Peřina Jr., J.; Haderka, Ondřej; Allevi, A.; Bondani, M.

    2016-01-01

    Roč. 6, Feb (2016), 1-8, č. článku 22320. ISSN 2045-2322 R&D Projects: GA ČR GAP205/12/0382 Institutional support: RVO:68378271 Keywords : dynamics of intense * twin beams * pump-depleted parametric * down-conversion * coherence Subject RIV: BH - Optics, Masers, Lasers Impact factor: 4.259, year: 2016

  5. Rotational characterization of methyl methacrylate: Internal dynamics and structure determination

    Science.gov (United States)

    Herbers, Sven; Wachsmuth, Dennis; Obenchain, Daniel A.; Grabow, Jens-Uwe

    2018-01-01

    Rotational constants, Watson's S centrifugal distortion coefficients, and internal rotation parameters of the two most stable conformers of methyl methacrylate were retrieved from the microwave spectrum. Splittings of rotational energy levels were caused by two non equivalent methyl tops. Constraining the centrifugal distortion coefficients and internal rotation parameters to the values of the main isotopologues, the rotational constants of all single substituted 13C and 18O isotopologues were determined. From these rotational constants the substitution structures and semi-empirical zero point structures of both conformers were precisely determined.

  6. An outline of military technological dynamics as restraints for acquisition, international cooperation and domestic technological development

    Directory of Open Access Journals (Sweden)

    Édison Renato Silva

    2014-12-01

    Full Text Available The expectation that technological returns from defense expenditure through acquisition, international cooperation and domestic research would further national development underappreciates the different technological dynamic of the armed services. This paper outlines the technological dynamic the stems from fighting in the air, at sea and on land, exemplifying consequences for the case of acquisition.

  7. International Workshop on Advanced Dynamics and Model Based Control of Structures and Machines

    CERN Document Server

    Belyaev, Alexander; Krommer, Michael

    2017-01-01

    The papers in this volume present and discuss the frontiers in the mechanics of controlled machines and structures. They are based on papers presented at the International Workshop on Advanced Dynamics and Model Based Control of Structures and Machines held in Vienna in September 2015. The workshop continues a series of international workshops held in Linz (2008) and St. Petersburg (2010).

  8. International Workshop on Mathematical Modeling of Tumor-Immune Dynamics

    CERN Document Server

    Kim, Peter; Mallet, Dann

    2014-01-01

    This collection of papers offers a broad synopsis of state-of-the-art mathematical methods used in modeling the interaction between tumors and the immune system. These papers were presented at the four-day workshop on Mathematical Models of Tumor-Immune System Dynamics held in Sydney, Australia from January 7th to January 10th, 2013. The workshop brought together applied mathematicians, biologists, and clinicians actively working in the field of cancer immunology to share their current research and to increase awareness of the innovative mathematical tools that are applicable to the growing field of cancer immunology. Recent progress in cancer immunology and advances in immunotherapy suggest that the immune system plays a fundamental role in host defense against tumors and could be utilized to prevent or cure cancer. Although theoretical and experimental studies of tumor-immune system dynamics have a long history, there are still many unanswered questions about the mechanisms that govern the interaction betwe...

  9. International Trade and Macroeconomic Dynamics with Heteroegenous Firms

    OpenAIRE

    Ghironi, Fabio; Melitz, Marc J

    2004-01-01

    We develop a stochastic, general equilibrium, two-country model of trade and macroeconomic dynamics. Productivity differs across individual, monopolistically competitive firms in each country. Firms face a sunk entry cost in the domestic market and both fixed and per-unit export costs. Only relatively more productive firms export. Exogenous shocks to aggregate productivity and entry or trade costs induce firms to enter and exit both their domestic and export markets, thus altering the composi...

  10. Review of selected dynamic material control functions for international safeguards

    International Nuclear Information System (INIS)

    Lowry, L.L.

    1980-09-01

    With the development of Dynamic Special Nuclear Material Accounting and Control systems used in nuclear manufacturing and reprocessing plants, there arises the question as to how these systems affect the IAEA inspection capabilities. The systems in being and under development provide information and control for a variety of purposes important to the plant operator, the safeguards purpose being one of them. This report attempts to judge the usefulness of these dynamic systems to the IAEA and have defined 12 functions that provide essential information to it. If the information acquired by these dynamic systems is to be useful to the IAEA, the inspectors must be able to independently verify it. Some suggestions are made as to how this might be done. But, even if it should not be possible to verify all the data, the availability to the IAEA of detailed, simultaneous, and plant-wide information would tend to inhibit a plant operator from attempting to generate a floating or fictitious inventory. Suggestions are made that might be helpful in the design of future software systems, an area which has proved to be fatally deficient in some systems and difficult in all

  11. Dynamic managerial capability of technology-based international new ventures

    DEFF Research Database (Denmark)

    Altshuler, Liliya

    2014-01-01

    case study of a technology-based INV conducted over the period of 3.5 years, starting 8 years into the firm’s history. This unique design has enabled close observation of the specific events and challenges the firm has been facing after its initial success, and of the aspects in the firm’s management...... to resource availability. The study takes the dynamic capability perspective and focuses on INVs’ management, which are seen as founders and builders of the processes, rules and structures that lay the basis for long-term competitive advantage for such firms. Based on the findings, specific aspects...

  12. Dynamic International Competitiveness of Transition Economies: The Case of Poland

    DEFF Research Database (Denmark)

    Nielsen, Jørgen Ulff-Møller

    2003-01-01

    This paper shows that the reform on the structures of the Polish economy has had an impressively fast effect on the numbers of different products this country exports to Western countries. The time path may well be described by a logistic curve. The change in the exports of this country may...... therefore be characterised by a widening, instead of a deepening in specialisation. The paper introduces a new empirical methodology to evaluate the dynamic changes in export activities of a country. The result of this new methodology is that quality competition is becoming increasingly important for Poland...

  13. Evolution of energy labelling: analysis of international dynamics

    International Nuclear Information System (INIS)

    Malandrino, Ornella; Roca, Emmanuele

    2005-01-01

    Currently there are large variety of tools that play a very important role in providing benchmarks for sustainability performance of products and guidance for consumers. The present paper analyses the most important programme related to energy labelling, a market based instrument mainly addressed to consumers, certifying that a specific product is energy efficient. Particular attention has been given to International and European Union Labels of the consumption of energy and other resources by household appliances, to the energy efficient labelling programmes for office equipment and the certification schemes of energy performance of buildings

  14. Internal Kink Mode Dynamics in High-β NSTX Plasmas

    International Nuclear Information System (INIS)

    Menard, J.E.; Bell, R.E.; Fredrickson, E.D.; Gates, D.A.; Kaye, S.M.; LeBlanc, B.P.; Medley, S.S.; Park, W.; Sabbagh, S.A.; Sontag, A.; Stutman, D.; Tritz, K.; Zhu, W.

    2004-01-01

    Saturated internal kink modes have been observed in many of the highest toroidal beta discharges of the National Spherical Torus Experiment (NSTX). These modes often cause rotation flattening in the plasma core, can degrade energy confinement, and in some cases contribute to the complete loss of plasma angular momentum and stored energy. Characteristics of the modes are measured using soft X-ray, kinetic profile, and magnetic diagnostics. Toroidal flows approaching Alfvenic speeds, island pressure peaking, and enhanced viscous and diamagnetic effects associated with high-beta may contribute to mode nonlinear stabilization. These saturation mechanisms are investigated for NSTX parameters and compared to experimental data

  15. Internal kink mode dynamics in high-β NSTX plasmas

    International Nuclear Information System (INIS)

    Menard, J.E.; Bell, R.E.; Fredrickson, E.D.; Gates, D.A.; Kaye, S.M.; LeBlanc, B.P.; Medley, S.S.; Park, W.; Sabbagh, S.A.; Sontag, A.; Zhu, W.; Stutman, D.; Tritz, K.

    2005-01-01

    Saturated internal kink modes have been observed in many of the highest toroidal beta discharges of the National Spherical Torus Experiment (NSTX). These modes often cause rotation flattening in the plasma core, can degrade energy confinement, and in some cases contribute to the complete loss of plasma angular momentum and stored energy. Characteristics of the modes are measured using soft X-ray, kinetic profile, and magnetic diagnostics. Toroidal flows approaching Alfvenic speeds, island pressure peaking, and enhanced viscous and diamagnetic effects associated with high-beta may contribute to mode non-linear stabilization. These saturation mechanisms are investigated for NSTX parameters and compared to experiment. (author)

  16. Effects of internal friction on contact formation dynamics of polymer chain

    Science.gov (United States)

    Bian, Yukun; Li, Peng; Zhao, Nanrong

    2018-04-01

    A theoretical framework is presented to study the contact formation dynamics of polymer chains, in accompany with an electron-transfer quenching. Based on a non-Markovian Smoluchowski equation supplemented with an exponential sink term, we derive the mean time of contact formation under Wilemski-Fixman approximation. Our particular attentions are paid to the effect of internal friction. We find out that internal friction induces a novel fractional viscosity dependence, which will become more remarkable as internal friction increases. Furthermore, we clarify that internal friction inevitably promotes a diffusion-controlled mechanism by slowing the chain relaxation. Finally, we apply our theory to rationalise the experimental investigation for contact formation of a single-stranded DNA. The theoretical results can reproduce the experimental data very well with quite reasonable estimation for the intrinsic parameters. Such good agreements clearly demonstrate the validity of our theory which has appropriately addressed the very role of internal friction to the relevant dynamics.

  17. Size measuring techniques as tool to monitor pea proteins intramolecular crosslinking by transglutaminase treatment.

    Science.gov (United States)

    Djoullah, Attaf; Krechiche, Ghali; Husson, Florence; Saurel, Rémi

    2016-01-01

    In this work, techniques for monitoring the intramolecular transglutaminase cross-links of pea proteins, based on protein size determination, were developed. Sodium dodecyl sulfate-polyacrylamide gel electrophoresis profiles of transglutaminase-treated low concentration (0.01% w/w) pea albumin samples, compared to the untreated one (control), showed a higher electrophoretic migration of the major albumin fraction band (26 kDa), reflecting a decrease in protein size. This protein size decrease was confirmed, after DEAE column purification, by dynamic light scattering (DLS) where the hydrodynamic radius of treated samples appears to be reduced compared to the control one. Copyright © 2015 Elsevier Ltd. All rights reserved.

  18. Occupant-vehicle dynamics and the role of the internal model

    Science.gov (United States)

    Cole, David J.

    2018-05-01

    With the increasing need to reduce time and cost of vehicle development there is increasing advantage in simulating mathematically the dynamic interaction of a vehicle and its occupant. The larger design space arising from the introduction of automated vehicles further increases the potential advantage. The aim of the paper is to outline the role of the internal model hypothesis in understanding and modelling occupant-vehicle dynamics, specifically the dynamics associated with direction and speed control of the vehicle. The internal model is the driver's or passenger's understanding of the vehicle dynamics and is thought to be employed in the perception, cognition and action processes of the brain. The internal model aids the estimation of the states of the vehicle from noisy sensory measurements. It can also be used to optimise cognitive control action by predicting the consequence of the action; thus model predictive control (MPC) theory provides a foundation for modelling the cognition process. The stretch reflex of the neuromuscular system also makes use of the prediction of the internal model. Extensions to the MPC approach are described which account for: interaction with an automated vehicle; robust control; intermittent control; and cognitive workload. Further work to extend understanding of occupant-vehicle dynamic interaction is outlined. This paper is based on a keynote presentation given by the author to the 13th International Symposium on Advanced Vehicle Control (AVEC) conference held in Munich, September 2016.

  19. Quantum master equation for collisional dynamics of massive particles with internal degrees of freedom

    International Nuclear Information System (INIS)

    Smirne, Andrea; Vacchini, Bassano

    2010-01-01

    We address the microscopic derivation of a quantum master equation in Lindblad form for the dynamics of a massive test particle with internal degrees of freedom, interacting through collisions with a background ideal gas. When either internal or center-of-mass degrees of freedom can be treated classically, previously established equations are obtained as special cases. If in an interferometric setup the internal degrees of freedom are not detected at the output, the equation can be recast in the form of a generalized Lindblad structure, which describes non-Markovian effects. The effect of internal degrees of freedom on center-of-mass decoherence is considered in this framework.

  20. Comparison of the Internal Dynamics of Metalloproteases Provides New Insights on Their Function and Evolution.

    Directory of Open Access Journals (Sweden)

    Henrique F Carvalho

    Full Text Available Metalloproteases have evolved in a vast number of biological systems, being one of the most diverse types of proteases and presenting a wide range of folds and catalytic metal ions. Given the increasing understanding of protein internal dynamics and its role in enzyme function, we are interested in assessing how the structural heterogeneity of metalloproteases translates into their dynamics. Therefore, the dynamical profile of the clan MA type protein thermolysin, derived from an Elastic Network Model of protein structure, was evaluated against those obtained from a set of experimental structures and molecular dynamics simulation trajectories. A close correspondence was obtained between modes derived from the coarse-grained model and the subspace of functionally-relevant motions observed experimentally, the later being shown to be encoded in the internal dynamics of the protein. This prompted the use of dynamics-based comparison methods that employ such coarse-grained models in a representative set of clan members, allowing for its quantitative description in terms of structural and dynamical variability. Although members show structural similarity, they nonetheless present distinct dynamical profiles, with no apparent correlation between structural and dynamical relatedness. However, previously unnoticed dynamical similarity was found between the relevant members Carboxypeptidase Pfu, Leishmanolysin, and Botulinum Neurotoxin Type A, despite sharing no structural similarity. Inspection of the respective alignments shows that dynamical similarity has a functional basis, namely the need for maintaining proper intermolecular interactions with the respective substrates. These results suggest that distinct selective pressure mechanisms act on metalloproteases at structural and dynamical levels through the course of their evolution. This work shows how new insights on metalloprotease function and evolution can be assessed with comparison schemes that

  1. International energy market dynamics: a modelling approach. Tome 1

    International Nuclear Information System (INIS)

    Nachet, S.

    1996-01-01

    This work is an attempt to model international energy market and reproduce the behaviour of both energy demand and supply. Energy demand was represented using sector versus source approach. For developing countries, existing link between economic and energy sectors were analysed. Energy supply is exogenous for energy sources other than oil and natural gas. For hydrocarbons, exploration-production process was modelled and produced figures as production yield, exploration effort index, etc. The model built is econometric and is solved using a software that was constructed for this purpose. We explore the energy market future using three scenarios and obtain projections by 2010 for energy demand per source and oil natural gas supply per region. Economic variables are used to produce different indicators as energy intensity, energy per capita, etc. (author). 378 refs., 26 figs., 35 tabs., 11 appends

  2. International energy market dynamics: a modelling approach. Tome 2

    International Nuclear Information System (INIS)

    Nachet, S.

    1996-01-01

    This work is an attempt to model international energy market and reproduce the behaviour of both energy demand and supply. Energy demand was represented using sector versus source approach. For developing countries, existing link between economic and energy sectors were analysed. Energy supply is exogenous for energy sources other than oil and natural gas. For hydrocarbons, exploration-production process was modelled and produced figures as production yield, exploration effort index, ect. The model build is econometric and is solved using a software that was constructed for this purpose. We explore the energy market future using three scenarios and obtain projections by 2010 for energy demand per source and oil and natural gas supply per region. Economic variables are used to produce different indicators as energy intensity, energy per capita, etc. (author). 378 refs., 26 figs., 35 tabs., 11 appends

  3. 14th International Conference on Nonequilibrium Carrier Dynamics in Semiconductors

    CERN Document Server

    Saraniti, M; Nonequilibrium Carrier Dynamics in Semiconductors

    2006-01-01

    International experts gather every two years at this established conference to discuss recent developments in theory and experiment in non-equilibrium transport phenomena. These developments have been the driving force behind the spectacular advances in semiconductor physics and devices over the last few decades. Originally known as "Hot Carriers in Semiconductors," the 14th conference in the series covered a wide spectrum of traditional topics dealing with non-equilibrium phenomena, ranging from quantum transport to optical phenomena in mesoscopic and nano-scale structures. Particular attention was given this time to emerging areas of this rapidly evolving field, with many sessions covering terahertz devices, high field transport in nitride semiconductors, spintronics, molecular electronics, and bioelectronics applications.

  4. 12th International Conference of Dynamical Systems-Theory and Applications

    CERN Document Server

    Applied Non-Linear Dynamical Systems

    2014-01-01

    The book is a collection of contributions devoted to analytical, numerical and experimental techniques of dynamical systems, presented at the International Conference on Dynamical Systems: Theory and Applications, held in Łódź, Poland on December 2-5, 2013. The studies give deep insight into both the theory and applications of non-linear dynamical systems, emphasizing directions for future research. Topics covered include: constrained motion of mechanical systems and tracking control; diversities in the inverse dynamics; singularly perturbed ODEs with periodic coefficients; asymptotic solutions to the problem of vortex structure around a cylinder; investigation of the regular and chaotic dynamics; rare phenomena and chaos in power converters; non-holonomic constraints in wheeled robots; exotic bifurcations in non-smooth systems; micro-chaos; energy exchange of coupled oscillators; HIV dynamics; homogenous transformations with applications to off-shore slender structures; novel approaches to a qualitative s...

  5. Investigations Into Internal and External Aspects of Dynamic Agent-Environment Couplings

    Science.gov (United States)

    Dautenhahn, Kerstin

    This paper originates from my work on `social agents'. An issue which I consider important to this kind of research is the dynamic coupling of an agent with its social and non-social environment. I hypothesize `internal dynamics' inside an agent as a basic step towards understanding. The paper therefore focuses on the internal and external dynamics which couple an agent to its environment. The issue of embodiment in animals and artifacts and its relation to `social dynamics' is discussed first. I argue that embodiment is linked to a concept of a body and is not necessarily given when running a control program on robot hardware. I stress the individual characteristics of an embodied cognitive system, as well as its social embeddedness. I outline the framework of a physical-psychological state space which changes dynamically in a self-modifying way as a holistic approach towards embodied human and artificial cognition. This framework is meant to discuss internal and external dynamics of an embodied, natural or artificial agent. In order to stress the importance of a dynamic memory I introduce the concept of an `autobiographical agent'. The second part of the paper gives an example of the implementation of a physical agent, a robot, which is dynamically coupled to its environment by balancing on a seesaw. For the control of the robot a behavior-oriented approach using the dynamical systems metaphor is used. The problem is studied through building a complete and co-adapted robot-environment system. A seesaw which varies its orientation with one or two degrees of freedom is used as the artificial `habitat'. The problem of stabilizing the body axis by active motion on a seesaw is solved by using two inclination sensors and a parallel, behavior-oriented control architecture. Some experiments are described which demonstrate the exploitation of the dynamics of the robot-environment system.

  6. Internal variability of a dynamically downscaled climate over North America

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Jiali; Bessac, Julie; Kotamarthi, Rao; Constantinescu, Emil; Drewniak, Beth

    2017-09-08

    This study investigates the internal variability (IV) of a regional climate model, and considers the impacts of horizontal resolution and spectral nudging on the IV. A 16-member simulation ensemble was conducted using the Weather Research Forecasting model for three model configurations. Ensemble members included simulations at spatial resolutions of 50 km and 12 km without spectral nudging and simulations at a spatial resolution of 12 km with spectral nudging. All the simulations were generated over the same domain, which covered much of North America. The degree of IV was measured as the spread between the individual members of the ensemble during the integration period. The IV of the 12 km simulation with spectral nudging was also compared with a future climate change simulation projected by the same model configuration. The variables investigated focus on precipitation and near-surface air temperature. While the IVs show a clear annual cycle with larger values in summer and smaller values in winter, the seasonal IV is smaller for a 50-km spatial resolution than for a 12-km resolution when nudging is not applied. Applying a nudging technique to the 12-km simulation reduces the IV by a factor of two, and produces smaller IV than the simulation at 50 km without nudging. Applying a nudging technique also changes the geographic distributions of IV in all examined variables. The IV is much smaller than the inter-annual variability at seasonal scales for regionally averaged temperature and precipitation. The IV is also smaller than the projected changes in air-temperature for the mid- and late 21st century. However, the IV is larger than the projected changes in precipitation for the mid- and late 21st century.

  7. Internal variability of a dynamically downscaled climate over North America

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Jiali; Bessac, Julie; Kotamarthi, Rao; Constantinescu, Emil; Drewniak, Beth

    2017-09-08

    This study investigates the internal variability (IV) of a regional climate model, and considers the impacts of horizontal resolution and spectral nudging on the IV. A 16-member simulation ensemble was conducted using the Weather Research Forecasting model for three model configurations. Ensemble members included simulations at spatial resolutions of 50 and 12 km without spectral nudging and simulations at a spatial resolution of 12 km with spectral nudging. All the simulations were generated over the same domain, which covered much of North America. The degree of IV was measured as the spread between the individual members of the ensemble during the integration period. The IV of the 12 km simulation with spectral nudging was also compared with a future climate change simulation projected by the same model configuration. The variables investigated focus on precipitation and near-surface air temperature. While the IVs show a clear annual cycle with larger values in summer and smaller values in winter, the seasonal IV is smaller for a 50-km spatial resolution than for a 12-km resolution when nudging is not applied. Applying a nudging technique to the 12-km simulation reduces the IV by a factor of two, and produces smaller IV than the simulation at 50 km without nudging. Applying a nudging technique also changes the geographic distributions of IV in all examined variables. The IV is much smaller than the inter-annual variability at seasonal scales for regionally averaged temperature and precipitation. The IV is also smaller than the projected changes in air-temperature for the mid- and late twenty-first century. However, the IV is larger than the projected changes in precipitation for the mid- and late twenty-first century.

  8. Internal variability of a dynamically downscaled climate over North America

    Science.gov (United States)

    Wang, Jiali; Bessac, Julie; Kotamarthi, Rao; Constantinescu, Emil; Drewniak, Beth

    2017-09-01

    This study investigates the internal variability (IV) of a regional climate model, and considers the impacts of horizontal resolution and spectral nudging on the IV. A 16-member simulation ensemble was conducted using the Weather Research Forecasting model for three model configurations. Ensemble members included simulations at spatial resolutions of 50 and 12 km without spectral nudging and simulations at a spatial resolution of 12 km with spectral nudging. All the simulations were generated over the same domain, which covered much of North America. The degree of IV was measured as the spread between the individual members of the ensemble during the integration period. The IV of the 12 km simulation with spectral nudging was also compared with a future climate change simulation projected by the same model configuration. The variables investigated focus on precipitation and near-surface air temperature. While the IVs show a clear annual cycle with larger values in summer and smaller values in winter, the seasonal IV is smaller for a 50-km spatial resolution than for a 12-km resolution when nudging is not applied. Applying a nudging technique to the 12-km simulation reduces the IV by a factor of two, and produces smaller IV than the simulation at 50 km without nudging. Applying a nudging technique also changes the geographic distributions of IV in all examined variables. The IV is much smaller than the inter-annual variability at seasonal scales for regionally averaged temperature and precipitation. The IV is also smaller than the projected changes in air-temperature for the mid- and late twenty-first century. However, the IV is larger than the projected changes in precipitation for the mid- and late twenty-first century.

  9. Internal variability of a dynamically downscaled climate over North America

    Science.gov (United States)

    Wang, Jiali; Bessac, Julie; Kotamarthi, Rao; Constantinescu, Emil; Drewniak, Beth

    2018-06-01

    This study investigates the internal variability (IV) of a regional climate model, and considers the impacts of horizontal resolution and spectral nudging on the IV. A 16-member simulation ensemble was conducted using the Weather Research Forecasting model for three model configurations. Ensemble members included simulations at spatial resolutions of 50 and 12 km without spectral nudging and simulations at a spatial resolution of 12 km with spectral nudging. All the simulations were generated over the same domain, which covered much of North America. The degree of IV was measured as the spread between the individual members of the ensemble during the integration period. The IV of the 12 km simulation with spectral nudging was also compared with a future climate change simulation projected by the same model configuration. The variables investigated focus on precipitation and near-surface air temperature. While the IVs show a clear annual cycle with larger values in summer and smaller values in winter, the seasonal IV is smaller for a 50-km spatial resolution than for a 12-km resolution when nudging is not applied. Applying a nudging technique to the 12-km simulation reduces the IV by a factor of two, and produces smaller IV than the simulation at 50 km without nudging. Applying a nudging technique also changes the geographic distributions of IV in all examined variables. The IV is much smaller than the inter-annual variability at seasonal scales for regionally averaged temperature and precipitation. The IV is also smaller than the projected changes in air-temperature for the mid- and late twenty-first century. However, the IV is larger than the projected changes in precipitation for the mid- and late twenty-first century.

  10. Dynamic and Thermodynamic Examination of a Two-Stroke Internal Combustion Engine

    OpenAIRE

    İPCİ, Duygu; KARABULUT, Halit

    2016-01-01

    In this study the combined dynamic and thermodynamic analysis of a two-stroke internal combustion engine was carried out. The variation of the heat, given to the working fluid during the heating process of the thermodynamic cycle, was modeled with the Gaussian function. The dynamic model of the piston driving mechanism was established by means of nine equations, five of them are motion equations and four of them are kinematic relations. Equations are solved by using a numerical method based o...

  11. Is the Potential for International Diversification Disappearing? A Dynamic Copula Approach

    DEFF Research Database (Denmark)

    Christoffersen, Peter; Errunza, Vihang; Jacobs, Kris

    International equity markets are characterized by nonlinear dependence and asymmetries. We propose a new dynamic asymmetric copula model to capture long-run and short-run dependence, multivariate nonnormality, and asymmetries in large cross-sections. We find that copula correlations have increased...... and nonlinear dependence. The bene…fits from international diversi…cation have reduced over time, drastically so for DMs. EMs still offer signi…cant diversi…cation bene…ts, especially during large market downturns....

  12. Intramolecular hydrogen bonding in malonaldehyde and its radical analogues.

    Science.gov (United States)

    Lin, Chen; Kumar, Manoj; Finney, Brian A; Francisco, Joseph S

    2017-09-28

    High level Brueckner doubles with triples correction method-based ab initio calculations have been used to investigate the nature of intramolecular hydrogen bonding and intramolecular hydrogen atom transfer in cis-malonaldehyde (MA) and its radical analogues. The radicals considered here are the ones that correspond to the homolytic cleavage of C-H bonds in cis-MA. The results suggest that cis-MA and its radical analogues, cis-MA RS , and cis-MA RA , both exist in planar geometry. The calculated intramolecular O-H⋯O=C bond in cis-MA is shorter than that in the radical analogues. The intramolecular hydrogen bond in cis-MA is stronger than in its radicals by at least 3.0 kcal/mol. The stability of a cis-malonaldehyde radical correlates with the extent of electron spin delocalization; cis-MA RA , in which the radical spin is more delocalized, is the most stable MA radical, whereas cis-MA RS , in which the radical spin is strongly localized, is the least stable radical. The natural bond orbital analysis indicates that the intramolecular hydrogen bonding (O⋯H⋯O) in cis-malonaldehyde radicals is stabilized by the interaction between the lone pair orbitals of donor oxygen and the σ * orbital of acceptor O-H bond (n → σ * OH ). The calculated barriers indicate that the intramolecular proton transfer in cis-MA involves 2.2 kcal/mol lower barrier than that in cis-MA RS .

  13. Role of Reynolds stress and toroidal momentum transport in the dynamics of internal transport barriers

    International Nuclear Information System (INIS)

    Kim, S. S.; Jhang, Hogun; Diamond, P. H.

    2012-01-01

    We study the interplay between intrinsic rotation and internal transport barrier (ITB) dynamics through the dynamic change of the parallel Reynolds stress. Global flux-driven gyrofluid simulations are used for this study. In particular, we investigate the role of parallel velocity gradient instability (PVGI) in the ITB formation and the back transition. It is found that the excitation of PVGI is followed by a change in the Reynolds stress which drives a momentum redistribution. This significantly influences E×B shear evolution and subsequent ITB dynamics. Nonlocal interactions among fluctuations are also observed during the PVGI excitation, resulting in turbulence suppression at the ITB.

  14. Gating based on internal/external signals with dynamic correlation updates

    International Nuclear Information System (INIS)

    Wu Huanmei; Zhao Qingya; Berbeco, Ross I; Nishioka, Seiko; Shirato, Hiroki; Jiang, Steve B

    2008-01-01

    Precise localization of mobile tumor positions in real time is critical to the success of gated radiotherapy. Tumor positions are usually derived from either internal or external surrogates. Fluoroscopic gating based on internal surrogates, such as implanted fiducial markers, is accurate however requiring a large amount of imaging dose. Gating based on external surrogates, such as patient abdominal surface motion, is non-invasive however less accurate due to the uncertainty in the correlation between tumor location and external surrogates. To address these complications, we propose to investigate an approach based on hybrid gating with dynamic internal/external correlation updates. In this approach, the external signal is acquired at high frequency (such as 30 Hz) while the internal signal is sparsely acquired (such as 0.5 Hz or less). The internal signal is used to validate and update the internal/external correlation during treatment. Tumor positions are derived from the external signal based on the newly updated correlation. Two dynamic correlation updating algorithms are introduced. One is based on the motion amplitude and the other is based on the motion phase. Nine patients with synchronized internal/external motion signals are simulated retrospectively to evaluate the effectiveness of hybrid gating. The influences of different clinical conditions on hybrid gating, such as the size of gating windows, the optimal timing for internal signal acquisition and the acquisition frequency are investigated. The results demonstrate that dynamically updating the internal/external correlation in or around the gating window will reduce false positive with relatively diminished treatment efficiency. This improvement will benefit patients with mobile tumors, especially greater for early stage lung cancers, for which the tumors are less attached or freely floating in the lung.

  15. Gating based on internal/external signals with dynamic correlation updates

    Energy Technology Data Exchange (ETDEWEB)

    Wu Huanmei [Purdue School of Engineering and Technology, Indiana University School of Informatics, IUPUI, Indianapolis, IN (United States); Zhao Qingya [School of Health Sciences, Purdue University, West Lafayette, IN (United States); Berbeco, Ross I [Department of Radiation Oncology, Dana-Farber/Brigham and Womens Cancer Center and Harvard Medical School, Boston, MA (United States); Nishioka, Seiko [NTT East-Japan Sapporo Hospital, Sapporo (Japan); Shirato, Hiroki [Hokkaido University Graduate School of Medicine, Sapporo (Japan); Jiang, Steve B [Department of Radiation Oncology, School of Medicine, University of California, San Diego, CA (United States)], E-mail: hw9@iupui.edu, E-mail: sbjiang@ucsd.edu

    2008-12-21

    Precise localization of mobile tumor positions in real time is critical to the success of gated radiotherapy. Tumor positions are usually derived from either internal or external surrogates. Fluoroscopic gating based on internal surrogates, such as implanted fiducial markers, is accurate however requiring a large amount of imaging dose. Gating based on external surrogates, such as patient abdominal surface motion, is non-invasive however less accurate due to the uncertainty in the correlation between tumor location and external surrogates. To address these complications, we propose to investigate an approach based on hybrid gating with dynamic internal/external correlation updates. In this approach, the external signal is acquired at high frequency (such as 30 Hz) while the internal signal is sparsely acquired (such as 0.5 Hz or less). The internal signal is used to validate and update the internal/external correlation during treatment. Tumor positions are derived from the external signal based on the newly updated correlation. Two dynamic correlation updating algorithms are introduced. One is based on the motion amplitude and the other is based on the motion phase. Nine patients with synchronized internal/external motion signals are simulated retrospectively to evaluate the effectiveness of hybrid gating. The influences of different clinical conditions on hybrid gating, such as the size of gating windows, the optimal timing for internal signal acquisition and the acquisition frequency are investigated. The results demonstrate that dynamically updating the internal/external correlation in or around the gating window will reduce false positive with relatively diminished treatment efficiency. This improvement will benefit patients with mobile tumors, especially greater for early stage lung cancers, for which the tumors are less attached or freely floating in the lung.

  16. Simulation of the removal of NET internal components with dynamic modeling software

    International Nuclear Information System (INIS)

    Becquet, M.; Crutzen, Y.R.; Farfaletti-Casali, F.

    1989-01-01

    The replacement of the internal plasma-facing components (first-wall and blanket segments) for maintenance or at the end of their lifetime is an important aspect of the design of the next European torus (NET) and of the remote handling procedures. The first phase of development of the design software tool INVDYN (inverse dynamics) is presented, which will allow optimization of the movements of the internal segments during replacement, taking into account inertial effects and structural deformations. A first analysis of the removal of one NET internal segment provides, for a defined trajectory, the required generalized forces that must be applied on the crane system

  17. Politics and Graduate Medical Education in Internal Medicine: A Dynamic Landscape.

    Science.gov (United States)

    Wardrop, Richard M; Berkowitz, Lee R

    2017-02-01

    The promotion of change and growth within medical education is oftentimes the result of a complex mix of societal, cultural and economic forces. Graduate medical education in internal medicine is not immune to these forces. Several entities and organizations can be identified as having a major influence on internal medicine training and graduate medical education as a whole. We have reviewed how this is effectively accomplished through these entities and organizations. The result is a constantly changing and dynamic landscape for internal medicine training. Copyright © 2017 Southern Society for Clinical Investigation. Published by Elsevier Inc. All rights reserved.

  18. Internal kinematics and dynamical models of dwarf spheroidal galaxies around the Milky Way

    NARCIS (Netherlands)

    Battaglia, Giuseppina; Helmi, Amina; Breddels, Maarten

    We review our current understanding of the internal dynamical properties of the dwarf spheroidal galaxies surrounding the Milky Way. These are the most dark matter dominated galaxies, and as such may be considered ideal laboratories to test the current concordance cosmological model, and in

  19. Dynamics of Context-Dependent Recall: An Examination of Internal and External Context Change

    Science.gov (United States)

    Unsworth, Nash; Spillers, Gregory J.; Brewer, Gene A.

    2012-01-01

    Retrieval dynamics in context-dependent recall were explored via manipulations of external and internal context in two experiments. Participants were tested in either the same or different context as the material was learned in and correct recalls, errors, and recall latency measures were examined. In both experiments changes in context resulted…

  20. Study on dynamic characteristics of reduced analytical model for PWR reactor internal structures

    International Nuclear Information System (INIS)

    Yoo, Bong; Lee, Jae Han; Kim, Jong Bum; Koo, Kyeong Hoe

    1993-01-01

    The objective of this study is to establish the procedure of the reduced analytical modeling technique for the PWR reactor internal(RI) structures and to carry out the sensitivity study of the dynamic characteristics of the structures by varying the structural parameters such as the stiffness, the mass and the damping. Modeling techniques for the PWR reactor internal structures and computer programs used for the dynamic analysis of the reactor internal structures are briefly investigated. Among the many components of RI structures, the dynamic characteristics for CSB was performed. The sensitivity analysis of the dynamic characteristics for the reduced analytical model considering the variations of the stiffnesses for the lower and upper flanges of the CSB and for the RV Snubber were performed to improve the dynamic characteristics of the RI structures against the external loadings given. In order to enhance the structural design margin of the RI components, the nonlinear time history analyses were attempted for the RI reduced models to compare the structural responses between the reference model and the modified one. (Author)

  1. The dynamic interdependence of international financial markets: An empirical study on twenty-seven stock markets

    Science.gov (United States)

    Zhang, Xingwei; Zheng, Xiaolong; Zeng, Daniel Dajun

    2017-04-01

    In this paper, we aim to investigate the dynamic interdependence of international financial markets. Based on the data regarding daily returns of each market during the period 2006-2015 from Yahoo finance, we mainly focus on examining 27 markets from three continents, including Asia, America and Europe. By checking the dynamic interdependence between those markets, we find that markets from different continents have strong correlation at specific time shift. We also obtain that markets from different continents not only have a strong linkage with others at same day, but at a delay of one day, especially between Asia, Europe and Asia, America. In addition, we further analyze the time-varying influence strength between each two continents and observe that this value has abnormal changes during the financial crisis. These findings can provide us significant insights to understand the underlying dynamic interdependency of international financial markets and further help us make corresponding reasonable decisions.

  2. Evaluation of intramolecular charge transfer state of 4-N, N ...

    Indian Academy of Sciences (India)

    Abstract. Intramolecular charge transfer of 4-N,N-dimethylamino cinnamaldehyde (DMACA) in vacuum and in five different aprotic solvents has been studied by using time-dependent density functional theory. (TDDFT). Polarizable continuum model (PCM) was employed to consider solvent–solute interactions. The potential ...

  3. Intramolecular inverse electron demand Diels-Alder reactions of pyrimidines

    NARCIS (Netherlands)

    Frissen, A.E.

    1990-01-01

    This thesis deals with the intramolecular inverse electron demand Diels-Alder reaction of pyrimidines. The main objective of the study was to investigate the synthetic applicability of this reaction and to get more insight in the electronic and steric effects which determine the reactivity

  4. OH stretching frequencies in systems with intramolecular hydrogen bonds

    DEFF Research Database (Denmark)

    Spanget-Larsen, Jens; Hansen, Bjarke Knud Vilster; Hansen, Poul Erik

    2011-01-01

    OH stretching wavenumbers were investigated for 30 species with intramolecularly hydrogen bonded hydroxyl groups, covering the range from 3600 to ca. 1900 cm-1. Theoretical wavenumbers were predicted with B3LYP/6-31G(d) density functional theory using the standard harmonic approximation, as well...

  5. Preparation of CN /Carbon Nanotube Intramolecular Junctions by ...

    African Journals Online (AJOL)

    NICO

    intramolecular junctions composed of CNx with a bamboo-like structure and empty hollow carbon nanotubes were observed, ... and excellent thermal and mechanical properties.1,2 In recent .... tion of hexane, and the other segment with a curved compart- ... by an arrow lies at the interface of the junction between 'b' and.

  6. Excited-state intramolecular proton transfer of 2-acetylindan-1,3-dione studied by ultrafast absorption and fluorescence spectroscopy

    Directory of Open Access Journals (Sweden)

    Pramod Kumar Verma

    2016-03-01

    Full Text Available We employ transient absorption from the deep-UV to the visible region and fluorescence upconversion to investigate the photoinduced excited-state intramolecular proton-transfer dynamics in a biologically relevant drug molecule, 2-acetylindan-1,3-dione. The molecule is a ß-diketone which in the electronic ground state exists as exocyclic enol with an intramolecular H-bond. Upon electronic excitation at 300 nm, the first excited state of the exocyclic enol is initially populated, followed by ultrafast proton transfer (≈160 fs to form the vibrationally hot endocyclic enol. Subsequently, solvent-induced vibrational relaxation takes place (≈10 ps followed by decay (≈390 ps to the corresponding ground state.

  7. Simulations of ferrofluid dynamics: Rigid dipoles model versus particles with internal degrees of freedom

    International Nuclear Information System (INIS)

    Berkov, D.V.; Gorn, N.L.; Stock, D.

    2007-01-01

    For numerical studies of a ferrofluid dynamics we have developed a model which includes internal magnetic degrees of freedom of ferrofluid particles. Contrary to standard models, we take into account that the magnetocrystalline anisotropy of a ferrofluid particle material is finite, so that the particle moment is allowed to rotate with respect to the particle itself. Simulating magnetization relaxation of a ferrofluid after switching off the external field and comparing results with those obtained for rigid dipoles model, we demonstrate that for anisotropy typical for commonly used ferrofluid materials inclusion of 'magnetic' degrees of freedom is essential for a correct description of ferrofluid dynamics

  8. Self adaptive internal combustion engine control for hydrogen mixtures based on piezoelectric dynamic cylinder pressure transducers

    Energy Technology Data Exchange (ETDEWEB)

    Courteau, R.; Bose, T. K. [Universite du Quebec a Trois-Rivieres, Hydrogen Research Institute, Trois-Rivieres, PQ (Canada)

    2004-07-01

    An algorithm for self-adaptive tuning of an internal combustion engine is proposed, based on a Kalman filter operating on a few selected metrics of the dynamic pressure curve. Piezoelectric transducers are devices to monitor dynamic cylinder pressure; spark plugs with embedded piezo elements are now available to provide diagnostic engine functions. Such transducers are also capable of providing signals to the engine controller to perform auto tuning, a function that is considered very useful particularly in vehicles using alternative fuels whose characteristics frequently show variations between fill-ups. 2 refs., 2 figs.

  9. Novel effect of interplay of internal and external noise on the dynamics of calcium oscillations

    International Nuclear Information System (INIS)

    Li Hongying; Ma Juan

    2010-01-01

    Graphical abstract: When the external noise is small (D ≤ 0.8), R goes through a maximum at an optimal system size V, indicating the occurring of internal-noise stochastic resonance (INSR), and the curves become higher with the increases of D, which shows that INSR can be enhanced by the external noise in a certain range of external noise intensity ((D ≤ 0.8). If D > 0.8, R monotonically increases and the peak disappears. When D increases further, the R curve becomes lower. Research highlights: → External noise coherence resonance (ENCR) can be suppressed by internal noise. → Internal noise stochastic resonance (INSR) can be enhanced by external noise. → When INSR occurs, the optimal system size can be regulated by the external noise. - Abstract: Using a mesoscopic stochastic model, the effect of interplay of external and internal noise on the dynamics of calcium oscillations was studied. When the system was tuned near a Hopf bifurcation point and driven by external noise or internal noise only, the existence of external noise coherence resonance (ENCR) or internal-noise stochastic resonance (INSR) was found, respectively. When both of the noises were considered, it was found that ENCR could be suppressed by internal noise, while INSR could be enhanced by external noise in a certain range of external noise intensity. It was also interesting to note that the optimal system size can be regulated by the external noise when the INSR occurs. The cell system may adapt to adjust the optimal size according to the external noise, indicating some kind of self-tuning mechanism involved in stochastic calcium dynamics.

  10. Estimation of kinematic parameters in CALIFA galaxies: no-assumption on internal dynamics

    Science.gov (United States)

    García-Lorenzo, B.; Barrera-Ballesteros, J.; CALIFA Team

    2016-06-01

    We propose a simple approach to homogeneously estimate kinematic parameters of a broad variety of galaxies (elliptical, spirals, irregulars or interacting systems). This methodology avoids the use of any kinematical model or any assumption on internal dynamics. This simple but novel approach allows us to determine: the frequency of kinematic distortions, systemic velocity, kinematic center, and kinematic position angles which are directly measured from the two dimensional-distributions of radial velocities. We test our analysis tools using the CALIFA Survey

  11. Self adaptive internal combustion engine control for hydrogen mixtures based on piezoelectric dynamic cylinder pressure transducers

    International Nuclear Information System (INIS)

    Courteau, R.; Bose, T.K.

    2004-01-01

    Piezoelectric transducers offer an effective, non-intrusive way to monitor dynamic cylinder pressure in internal combustion engines. Devices dedicated to this purpose are appearing on the market, often in the form of spark plugs with embedded piezo elements. Dynamic cylinder pressure is typically used to provide diagnostic functions, or to help map an engine after it is designed. With the advent of powerful signal processor chips, it is now possible to embed enough computing power in the engine controller to perform auto tuning based on the signals provided by such transducers. Such functionality is very useful if the fuel characteristics vary between fill ups, as is often the case with alternative fuels. We propose here an algorithm for self-adaptive tuning based on a Kalman filter operating on a few selected metrics of the dynamic pressure curve. (author)

  12. Microbial Internal Storage Alters the Carbon Transformation in Dynamic Anaerobic Fermentation.

    Science.gov (United States)

    Ni, Bing-Jie; Batstone, Damien; Zhao, Bai-Hang; Yu, Han-Qing

    2015-08-04

    Microbial internal storage processes have been demonstrated to occur and play an important role in activated sludge systems under both aerobic and anoxic conditions when operating under dynamic conditions. High-rate anaerobic reactors are often operated at a high volumetric organic loading and a relatively dynamic profile, with large amounts of fermentable substrates. These dynamic operating conditions and high catabolic energy availability might also facilitate the formation of internal storage polymers by anaerobic microorganisms. However, so far information about storage under anaerobic conditions (e.g., anaerobic fermentation) as well as its consideration in anaerobic process modeling (e.g., IWA Anaerobic Digestion Model No. 1, ADM1) is still sparse. In this work, the accumulation of storage polymers during anaerobic fermentation was evaluated by batch experiments using anaerobic methanogenic sludge and based on mass balance analysis of carbon transformation. A new mathematical model was developed to describe microbial storage in anaerobic systems. The model was calibrated and validated by using independent data sets from two different anaerobic systems, with significant storage observed, and effectively simulated in both systems. The inclusion of the new anaerobic storage processes in the developed model allows for more successful simulation of transients due to lower accumulation of volatile fatty acids (correction for the overestimation of volatile fatty acids), which mitigates pH fluctuations. Current models such as the ADM1 cannot effectively simulate these dynamics due to a lack of anaerobic storage mechanisms.

  13. Mechanism of Intramolecular Rhodium- and Palladium-Catalyzed Alkene Alkoxyfunctionalizations

    KAUST Repository

    Vummaleti, Sai V. C.; Alghamdi, Miasser; Poater, Albert; Falivene, Laura; Scaranto, Jessica; Beetstra, Dirk J.; Morton, Jason G.; Cavallo, Luigi

    2015-01-01

    Density functional theory calculations have been used to investigate the reaction mechanism for the [Rh]-catalyzed intramolecular alkoxyacylation ([Rh] = [RhI(dppp)+] (dppp, 1,3-bis(diphenylphosphino)propane) and [Pd]/BPh3 dual catalytic system assisted intramolecular alkoxycyanation ([Pd] = Pd-Xantphos) using acylated and cyanated 2-allylphenol derivatives as substrates, respectively. Our results substantially confirm the proposed mechanism for both [Rh]- and [Pd]/ BPh3-mediated alkoxyfunctionalizations, offering a detailed geometrical and energetical understanding of all the elementary steps. Furthermore, for the [Rh]-mediated alkoxyacylation, our observations support the hypothesis that the quinoline group of the substrate is crucial to stabilize the acyl metal complex and prevent further decarbonylation. For [Pd]/BPh3-catalyzed alkoxycyanation, our findings clarify how the Lewis acid BPh3 cocatalyst accelerates the only slow step of the reaction, corresponding to the oxidative addition of the cyanate O-CN bond to the Pd center. © 2015 American Chemical Society.

  14. Mechanism of Intramolecular Rhodium- and Palladium-Catalyzed Alkene Alkoxyfunctionalizations

    KAUST Repository

    Vummaleti, Sai V. C.

    2015-11-13

    Density functional theory calculations have been used to investigate the reaction mechanism for the [Rh]-catalyzed intramolecular alkoxyacylation ([Rh] = [RhI(dppp)+] (dppp, 1,3-bis(diphenylphosphino)propane) and [Pd]/BPh3 dual catalytic system assisted intramolecular alkoxycyanation ([Pd] = Pd-Xantphos) using acylated and cyanated 2-allylphenol derivatives as substrates, respectively. Our results substantially confirm the proposed mechanism for both [Rh]- and [Pd]/ BPh3-mediated alkoxyfunctionalizations, offering a detailed geometrical and energetical understanding of all the elementary steps. Furthermore, for the [Rh]-mediated alkoxyacylation, our observations support the hypothesis that the quinoline group of the substrate is crucial to stabilize the acyl metal complex and prevent further decarbonylation. For [Pd]/BPh3-catalyzed alkoxycyanation, our findings clarify how the Lewis acid BPh3 cocatalyst accelerates the only slow step of the reaction, corresponding to the oxidative addition of the cyanate O-CN bond to the Pd center. © 2015 American Chemical Society.

  15. Intramolecular electron transfer in single-site-mutated azurins

    DEFF Research Database (Denmark)

    Farver, O; Skov, L K; Pascher, T

    1993-01-01

    . Natl. Acad. Sci. U.S.A. 86, 6968-6972]. The RSSR- radical produced in the above reaction was reoxidized in a slower intramolecular electron-transfer process (30-70 s-1 at 298 K) concomitant with a further reduction of the Cu(II) ion. The temperature dependence of the latter rates was determined......, lambda = 135 kJ mol-1 for the reorganization energy was derived. When Trp48, situated midway between the donor and the acceptor, was replaced by Leu or Met, only a small change in the rate of intramolecular electron transfer was observed, indicating that the aromatic residue in this position...... is apparently only marginally involved in electron transfer in wild-type azurin. Pathway calculations also suggest that a longer, through-backbone path is more efficient than the shorter one involving Trp48. The former pathway yields an exponential decay factor, beta, of 6.6 nm-1. Another mutation, raising...

  16. Structure and Intramolecular Proton Transfer of Alanine Radical Cations

    International Nuclear Information System (INIS)

    Lee, Gab Yong

    2012-01-01

    The structures of the four lowest alanine conformers, along with their radical cations and the effect of ionization on the intramolecular proton transfer process, are studied using the density functional theory and MP2 method. The energy order of the radical cations of alanine differs from that of the corresponding neutral conformers due to changes in the basicity of the NH 2 group upon ionization. Ionization favors the intramolecular proton transfer process, leading to a proton-transferred radical-cation structure, [NH 3 + -CHCH 3 -COO·], which contrasts with the fact that a proton-transferred zwitterionic conformer is not stable for a neutral alanine in the gas phase. The energy barrier during the proton transfer process is calculated to be about 6 kcal/mol

  17. Reaction Coordinate, Free Energy, and Rate of Intramolecular Proton Transfer in Human Carbonic Anhydrase II.

    Science.gov (United States)

    Paul, Sanjib; Paul, Tanmoy Kumar; Taraphder, Srabani

    2018-03-22

    The role of structure and dynamics of an enzyme has been investigated at three different stages of its function including the chemical event it catalyzes. A one-pot computational method has been designed for each of these stages on the basis of classical and/or quantum mechanical-molecular mechanical molecular dynamics and transition path sampling simulations. For a pair of initial and final states A and B separated by a high free-energy barrier, using a two-stage selection process, several collective variables (CVs) are identified that can delineate A and B. However, these CVs are found to exhibit strong cross-coupling over the transition paths. A set of mutually orthogonal order parameters is then derived from these CVs and an optimal reaction coordinate, r, determined applying half-trajectory likelihood maximization along with a Bayesian information criterion. The transition paths are also used to project the multidimensional free energy surface and barrier crossing dynamics along r. The proposed scheme has been applied to the rate-determining intramolecular proton transfer reaction of the well-known enzyme human carbonic anhydrase II. The potential of mean force, F( r), in the absence of the chemical step is found to reproduce earlier results on the equilibrium population of two side-chain orientations of key residue His-64. Estimation of rate constants, k, from mean first passage times for the three different stages of catalysis shows that the rate-determining step of intramolecular proton transfer occurs with k ≃ 1.0 × 10 6 s -1 , in close agreement with known experimental results.

  18. Emission Spectroscopy as a Probe into Photoinduced Intramolecular Electron Transfer in Polyazine Bridged Ru(II,Rh(III Supramolecular Complexes

    Directory of Open Access Journals (Sweden)

    Karen J. Brewer

    2010-08-01

    Full Text Available Steady-state and time-resolved emission spectroscopy are valuable tools to probe photochemical processes of metal-ligand, coordination complexes. Ru(II polyazine light absorbers are efficient light harvesters absorbing in the UV and visible with emissive 3MLCT excited states known to undergo excited state energy and electron transfer. Changes in emission intensity, energy or band-shape, as well as excited state lifetime, provide insight into excited state dynamics. Photophysical processes such as intramolecular electron transfer between electron donor and electron acceptor sub-units may be investigated using these methods. This review investigates the use of steady-state and time-resolved emission spectroscopy to measure excited state intramolecular electron transfer in polyazine bridged Ru(II,Rh(III supramolecular complexes. Intramolecular electron transfer in these systems provides for conversion of the emissive 3MLCT (metal-to-ligand charge transfer excited state to a non-emissive, but potentially photoreactive, 3MMCT (metal-to-metal charge transfer excited state. The details of the photophysics of Ru(II,Rh(III and Ru(II,Rh(III,Ru(II systems as probed by steady-state and time-resolved emission spectroscopy will be highlighted.

  19. Intramolecular Diels-Alder Reactions in Organic Synthesis

    OpenAIRE

    Sizemore, Nicholas Blandford Luke

    2014-01-01

    Intramolecular Diels-Alder (IMDA) reactions are an important class of reactions in synthetic organic chemistry for the rapid construction of polycyclic frameworks. Three classes of IMDA reactions were investigated synthetically and computationally: 1) all-carbon type 1 IMDA reactions, 2) N-acylnitroso type 2 IMDA reactions, and 3) cyano-azadiene IMDA reactions. The first class was implemented in research toward the total synthesis of maoecrystal Z and isopalhinine A. The second class was stud...

  20. A Dynamic Approach to the Analysis of Soft Power in International Relations

    Directory of Open Access Journals (Sweden)

    Chi Zhang

    2013-12-01

    Full Text Available This article discusses soft power in international relations and the soft power of China’s foreign policy in recent years. After presenting a critique of the soft power theory developed by Joseph S. Nye, the paper provides an alternative interpretation of soft power. The author proposes a dynamic analysis of soft power in international relations, and argues that whether a power resource is soft or hard depends on the perceptions and feelings of various actors in specific situations. Due to the varying degrees of acceptance, power can be divided into hard power, soft power and bargaining power. An analysis should look at the soft or hard effectiveness of a power resource from three perspectives–horizontally, vertically and relatively. Recently, the soft power of China’s foreign policy and international behavior has mainly been manifested in multilateralism, economic diplomacy and a good-neighborly policy.

  1. Role of internal demagnetizing field for the dynamics of a surface-modulated magnonic crystal

    Science.gov (United States)

    Langer, M.; Röder, F.; Gallardo, R. A.; Schneider, T.; Stienen, S.; Gatel, C.; Hübner, R.; Bischoff, L.; Lenz, K.; Lindner, J.; Landeros, P.; Fassbender, J.

    2017-05-01

    This work aims to demonstrate and understand the key role of local demagnetizing fields in hybrid structures consisting of a continuous thin film with a stripe modulation on top. To understand the complex spin dynamics of these structures, the magnonic crystal was reconstructed in two different ways—performing micromagnetic simulations based on the structural shape as well as based on the internal demagnetizing field, which both are mapped on the nanoscale using electron holography. The simulations yield the frequency-field dependence as well as the angular dependence revealing the governing role of the internal field landscape around the backward-volume geometry. Simple rules for the propagation vector and the mode localization are formulated in order to explain the calculated mode profiles. Treating internal demagnetizing fields equivalent to anisotropies, the complex angle-dependent spin-wave behavior is described for an in-plane rotation of the external field.

  2. Overcoming potential energy distortions in constrained internal coordinate molecular dynamics simulations

    Energy Technology Data Exchange (ETDEWEB)

    Kandel, Saugat; Salomon-Ferrer, Romelia; Larsen, Adrien B.; Vaidehi, Nagarajan, E-mail: nvaidehi@coh.org [Division of Immunology, Beckman Research Institute of the City of Hope, Duarte, California 91010 (United States); Jain, Abhinandan, E-mail: Abhi.Jain@jpl.nasa.gov [Jet Propulsion Laboratory, California Institute of Technology, 4800 Oak Grove Drive, Pasadena, California 91109 (United States)

    2016-01-28

    The Internal Coordinate Molecular Dynamics (ICMD) method is an attractive molecular dynamics (MD) method for studying the dynamics of bonded systems such as proteins and polymers. It offers a simple venue for coarsening the dynamics model of a system at multiple hierarchical levels. For example, large scale protein dynamics can be studied using torsional dynamics, where large domains or helical structures can be treated as rigid bodies and the loops connecting them as flexible torsions. ICMD with such a dynamic model of the protein, combined with enhanced conformational sampling method such as temperature replica exchange, allows the sampling of large scale domain motion involving high energy barrier transitions. Once these large scale conformational transitions are sampled, all-torsion, or even all-atom, MD simulations can be carried out for the low energy conformations sampled via coarse grained ICMD to calculate the energetics of distinct conformations. Such hierarchical MD simulations can be carried out with standard all-atom forcefields without the need for compromising on the accuracy of the forces. Using constraints to treat bond lengths and bond angles as rigid can, however, distort the potential energy landscape of the system and reduce the number of dihedral transitions as well as conformational sampling. We present here a two-part solution to overcome such distortions of the potential energy landscape with ICMD models. To alleviate the intrinsic distortion that stems from the reduced phase space in torsional MD, we use the Fixman compensating potential. To additionally alleviate the extrinsic distortion that arises from the coupling between the dihedral angles and bond angles within a force field, we propose a hybrid ICMD method that allows the selective relaxing of bond angles. This hybrid ICMD method bridges the gap between all-atom MD and torsional MD. We demonstrate with examples that these methods together offer a solution to eliminate the potential

  3. Proceedings of the international advisory committee on 'biomolecular dynamics instrument DNA' and the workshop on 'biomolecular dynamics backscattering spectrometers'

    International Nuclear Information System (INIS)

    Arai, Masatoshi; Aizawa, Kazuya; Nakajima, Kenji; Shibata, Kaoru; Takahashi, Nobuaki

    2008-08-01

    A workshop entitled 'Biomolecular Dynamics Backscattering Spectrometers' was held on February 27th - 29th, 2008 at J-PARC Center, Japan Atomic Energy Agency. This workshop was planned to be held for aiming to realize an innovative neutron backscattering instrument, namely DNA, in the MLF and thus four leading scientists in the field of neutron backscattering instruments were invited as the International Advisory Committee (IAC member: Dr. Dan Neumann (Chair); Prof. Ferenc Mezei; Dr. Hannu Mutka; Dr. Philip Tregenna-Piggott) for DNA from institutes in the United States, France and Switzerland, where backscattering instruments are in-service. It was therefore held in the form of lecture anterior and then in the form of the committee posterior. This report includes the executive summary of the IAC and materials of the presentations in the IAC and the workshop. (author)

  4. Phase transition and intramolecular hydrogen bonding in nitro derivatives of ortho-hydroxy acetophenones

    Science.gov (United States)

    Filarowski, A.; Kochel, A.; Koll, A.; Bator, G.; Mukherjee, S.

    2006-03-01

    The crystal structures of two ortho-hydroxy aryl ketones (5-chloro-3-nitro-2-hydroxyacetophenone, 5-methyl-3-nitro-2-hydroxyacetophenone and the complex 5-chloro-3-nitro-2-hydroxyacetophenone with 2-aminobenzoic acid (anthranilic acid)) were determined by X-ray diffraction. The existence of an intramolecular hydrogen bond of enol character between the hydroxyl and acetyl groups was found by the X-ray method. The enol character was also confirmed by DFT (B3LYP/6-31+G(d,p)) calculations. A phase transition was found at 138 K in 5-chloro-3-nitro-2-hydroxyacetophenone. This phase transition was investigated by differential scanning calorimetry (DSC), dilatometry, and the dielectric method. A study of the nitro-group dynamics in the ortho-hydroxy acetophenones was carried out with DFT (B3LYP/6-31+G(d,p)) calculations.

  5. Controlling Long-Lived Triplet Generation from Intramolecular Singlet Fission in the Solid State

    KAUST Repository

    Pace, Natalie A.

    2017-11-30

    The conjugated polymer poly(benzothiophene dioxide) (PBTDO1) has recently been shown to exhibit efficient intramolecular singlet fission in solution. In this paper, we investigate the role of intermolecular interactions in triplet separation dynamics after singlet fission. We use transient absorption spectroscopy to determine the singlet fission rate and triplet yield in two polymers differing only by side chain motif in both solution and the solid state. Whereas solid-state films show singlet fission rates identical to those measured in solution, the average lifetime of the triplet population increases dramatically, and is strongly dependent on side-chain identity. These results show that it may be necessary to carefully engineer the solid-state microstructure of these “singlet fission polymers” in order to produce the long-lived triplets needed to realize efficient photovoltaic devices.

  6. Controlling Long-Lived Triplet Generation from Intramolecular Singlet Fission in the Solid State

    KAUST Repository

    Pace, Natalie A.; Zhang, Weimin; Arias, Dylan H.; McCulloch, Iain; Rumbles, Garry; Johnson, Justin C.

    2017-01-01

    The conjugated polymer poly(benzothiophene dioxide) (PBTDO1) has recently been shown to exhibit efficient intramolecular singlet fission in solution. In this paper, we investigate the role of intermolecular interactions in triplet separation dynamics after singlet fission. We use transient absorption spectroscopy to determine the singlet fission rate and triplet yield in two polymers differing only by side chain motif in both solution and the solid state. Whereas solid-state films show singlet fission rates identical to those measured in solution, the average lifetime of the triplet population increases dramatically, and is strongly dependent on side-chain identity. These results show that it may be necessary to carefully engineer the solid-state microstructure of these “singlet fission polymers” in order to produce the long-lived triplets needed to realize efficient photovoltaic devices.

  7. PREFACE: International Symposium on Dynamic Deformation and Fracture of Advanced Materials (D2FAM 2013)

    Science.gov (United States)

    Silberschmidt, Vadim V.

    2013-07-01

    Intensification of manufacturing processes and expansion of usability envelopes of modern components and structures in many cases result in dynamic loading regimes that cannot be resented adequately employing quasi-static formulations of respective problems of solid mechanics. Specific features of dynamic deformation, damage and fracture processes are linked to various factors, most important among them being: a transient character of load application; complex scenarios of propagation, attenuation and reflection of stress waves in real materials, components and structures; strain-rate sensitivity of materials properties; various thermo-mechanical regimes. All these factors make both experimental characterisation and theoretical (analytical and numerical) analysis of dynamic deformation and fracture rather challenging; for instance, besides dealing with a spatial realisation of these processes, their evolution with time should be also accounted for. To meet these challenges, an International Symposium on Dynamic Deformation and Fracture of Advanced Materials D2FAM 2013 was held on 9-11 September 2013 in Loughborough, UK. Its aim was to bring together specialists in mechanics of materials, applied mathematics, physics, continuum mechanics, materials science as well as various areas of engineering to discuss advances in experimental and theoretical analysis, and numerical simulations of dynamic mechanical phenomena. Some 50 papers presented at the Symposium by researchers from 12 countries covered various topics including: high-strain-rate loading and deformation; dynamic fracture; impact and blast loading; high-speed penetration; impact fatigue; damping properties of advanced materials; thermomechanics of dynamic loading; stress waves in micro-structured materials; simulation of failure mechanisms and damage accumulation; processes in materials under dynamic loading; a response of components and structures to harsh environment. The materials discussed at D2FAM 2013

  8. Binaries traveling through a gaseous medium: dynamical drag forces and internal torques

    Energy Technology Data Exchange (ETDEWEB)

    Sánchez-Salcedo, F. J. [Instituto de Astronomía, Universidad Nacional Autónoma de México, Ciudad Universitaria, Apt. Postal 70 264, C.P. 04510, Mexico City (Mexico); Chametla, Raul O., E-mail: jsanchez@astro.unam.mx [Escuela Superior de Física y Matemáticas, Instituto Politécnico Nacional, UP Adolfo López Mateos, Mexico City (Mexico)

    2014-10-20

    Using time-dependent linear theory, we investigate the morphology of the gravitational wake induced by a binary, whose center of mass moves at velocity V{sub cm} against a uniform background of gas. For simplicity, we assume that the components of the binary are on circular orbits about their common center of mass. The consequences of dynamical friction is twofold. First, gas dynamical friction may drag the center of mass of the binary and cause the binary to migrate. Second, drag forces also induce a braking torque, which causes the orbits of the components of the binary to shrink. We compute the drag forces acting on one component of the binary due to the gravitational interaction with its own wake. We show that the dynamical friction force responsible for decelerating the center of mass of the binary is smaller than it is in the point-mass case because of the loss of gravitational focusing. We show that the braking internal torque depends on the Mach numbers of each binary component about their center of mass, and also on the Mach number of the center of mass of the binary. In general, the internal torque decreases with increasing the velocity of the binary relative to the ambient gas cloud. However, this is not always the case. We also mention the relevance of our results to the period distribution of binaries.

  9. Waiting time distribution revealing the internal spin dynamics in a double quantum dot

    Science.gov (United States)

    Ptaszyński, Krzysztof

    2017-07-01

    Waiting time distribution and the zero-frequency full counting statistics of unidirectional electron transport through a double quantum dot molecule attached to spin-polarized leads are analyzed using the quantum master equation. The waiting time distribution exhibits a nontrivial dependence on the value of the exchange coupling between the dots and the gradient of the applied magnetic field, which reveals the oscillations between the spin states of the molecule. The zero-frequency full counting statistics, on the other hand, is independent of the aforementioned quantities, thus giving no insight into the internal dynamics. The fact that the waiting time distribution and the zero-frequency full counting statistics give a nonequivalent information is associated with two factors. Firstly, it can be explained by the sensitivity to different timescales of the dynamics of the system. Secondly, it is associated with the presence of the correlation between subsequent waiting times, which makes the renewal theory, relating the full counting statistics and the waiting time distribution, no longer applicable. The study highlights the particular usefulness of the waiting time distribution for the analysis of the internal dynamics of mesoscopic systems.

  10. The case for an internal dynamics model versus equilibrium point control in human movement.

    Science.gov (United States)

    Hinder, Mark R; Milner, Theodore E

    2003-06-15

    The equilibrium point hypothesis (EPH) was conceived as a means whereby the central nervous system could control limb movements by a relatively simple shift in equilibrium position without the need to explicitly compensate for task dynamics. Many recent studies have questioned this view with results that suggest the formation of an internal dynamics model of the specific task. However, supporters of the EPH have argued that these results are not incompatible with the EPH and that there is no reason to abandon it. In this study, we have tested one of the fundamental predictions of the EPH, namely, equifinality. Subjects learned to perform goal-directed wrist flexion movements while a motor provided assistance in proportion to the instantaneous velocity. It was found that the subjects stopped short of the target on the trials where the magnitude of the assistance was randomly decreased, compared to the preceding control trials (P = 0.003), i.e. equifinality was not achieved. This is contrary to the EPH, which predicts that final position should not be affected by external loads that depend purely on velocity. However, such effects are entirely consistent with predictions based on the formation of an internal dynamics model.

  11. Preface: Special issue featuring papers from the International Conference on Nonequilibrium Carrier Dynamics in Semiconductors

    Science.gov (United States)

    Reggiani, L.; Bordone, P.; Brunetti, R.

    2004-02-01

    The International Conference on Nonequilibrium Carrier Dynamics in Semiconductors (HCIS-13) celebrates 30 years since it first took place in Modena. Nonequilibrium dynamics of charge carriers, pioneered by the hot-electron concept, is an important issue for understanding electro-optic transport properties in semiconductor materials and structures. In these 30 years several topics have matured, and new ones have emerged thus fertilizing the field with a variety of physical problems and new ideas. The history of the conference is summarized in the opening paper `30 years of HCIS'. The future of the conference seems secure considering the continued lively interest of the participants. The conference addressed eleven major topics which constitute the backbone of the proceedings and are summarized as follows: carrier transport in low dimensional and nanostructure systems, nonequilibrium carriers in superlattices and devices, small devices and related phenomena, carrier dynamics and fluctuations, carrier quantum dynamics, coherent/incoherent carrier dynamics of optical excitations and ultra-fast optical phenomena, nonlinear optical effects, transport in organic matter, semiconductor-based spintronics, coherent dynamics in solid state systems for quantum processing and communication, novel materials and devices. Nanometric space scale and femtosecond time scale represent the ultimate domains of theoretical, experimental and practical interest. Traditional fields such as bulk properties, quantum transport, fluctuations and chaotic phenomena, etc, have received thorough and continuous attention. Emerging fields from previous conferences, such as quantum processing and communication, have been better assessed. New fields, such as spintronics and electron transport in organic matter, have appeared for the first time. One plenary talk, 11 invited talks, 230 submitted abstracts covering all these topics constituted a single-session conference. Following scientific selection

  12. Analysis and Design of International Emission Trading Markets Applying System Dynamics Techniques

    Science.gov (United States)

    Hu, Bo; Pickl, Stefan

    2010-11-01

    The design and analysis of international emission trading markets is an important actual challenge. Time-discrete models are needed to understand and optimize these procedures. We give an introduction into this scientific area and present actual modeling approaches. Furthermore, we develop a model which is embedded in a holistic problem solution. Measures for energy efficiency are characterized. The economic time-discrete "cap-and-trade" mechanism is influenced by various underlying anticipatory effects. With a systematic dynamic approach the effects can be examined. First numerical results show that fair international emissions trading can only be conducted with the use of protective export duties. Furthermore a comparatively high price which evokes emission reduction inevitably has an inhibiting effect on economic growth according to our model. As it always has been expected it is not without difficulty to find a balance between economic growth and emission reduction. It can be anticipated using our System Dynamics model simulation that substantial changes must be taken place before international emissions trading markets can contribute to global GHG emissions mitigation.

  13. Theoretical study of γ-aminobutyric acid conformers: Intramolecular interactions and ionization energies

    Science.gov (United States)

    Wang, Ke-Dong; Wang, Mei-Ting; Meng, Ju

    2014-10-01

    Allowing for all combinations of internal single-bond rotamers, 1,296 unique trial structures of γ-Aminobutyric acid (GABA) are obtained. All of these structures are optimized at the M06-2X level of theory and a total of 68 local minimal conformers are found. The nine low-lying conformers are used for further studies. According to the calculated relative Gibbs free energies at M06-2X level of theory, we find that the dispersion is important for the relative energy of GABA. The intramolecular hydrogen bonds and hyperconjugative interaction and their effects on the conformational stability are studied. The results show that both of them have great influence on the conformers. The vertical ionization energies (VIE) are calculated and match the experimental data well. The results show that the neutral GABA in the gas phase is a multi-conformer system and at least four conformations exist.

  14. Output Tracking for Systems with Non-Hyperbolic and Near Non-Hyperbolic Internal Dynamics: Helicopter Hover Control

    Science.gov (United States)

    Devasia, Santosh

    1996-01-01

    A technique to achieve output tracking for nonminimum phase linear systems with non-hyperbolic and near non-hyperbolic internal dynamics is presented. This approach integrates stable inversion techniques, that achieve exact-tracking, with approximation techniques, that modify the internal dynamics to achieve desirable performance. Such modification of the internal dynamics is used (1) to remove non-hyperbolicity which an obstruction to applying stable inversion techniques and (2) to reduce large pre-actuation time needed to apply stable inversion for near non-hyperbolic cases. The method is applied to an example helicopter hover control problem with near non-hyperbolic internal dynamic for illustrating the trade-off between exact tracking and reduction of pre-actuation time.

  15. Characteristics of energy exchange between inter- and intramolecular degrees of freedom in crystalline 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) with implications for coarse-grained simulations of shock waves in polyatomic molecular crystals.

    Science.gov (United States)

    Kroonblawd, Matthew P; Sewell, Thomas D; Maillet, Jean-Bernard

    2016-02-14

    In this report, we characterize the kinetics and dynamics of energy exchange between intramolecular and intermolecular degrees of freedom (DoF) in crystalline 1,3,5-triamino-2,4,6-trinitrobenzene (TATB). All-atom molecular dynamics (MD) simulations are used to obtain predictions for relaxation from certain limiting initial distributions of energy between the intra- and intermolecular DoF. The results are used to parameterize a coarse-grained Dissipative Particle Dynamics at constant Energy (DPDE) model for TATB. Each TATB molecule in the DPDE model is represented as an all-atom, rigid-molecule mesoparticle, with explicit external (molecular translational and rotational) DoF and coarse-grained implicit internal (vibrational) DoF. In addition to conserving linear and angular momentum, the DPDE equations of motion conserve the total system energy provided that particles can exchange energy between their external and internal DoF. The internal temperature of a TATB molecule is calculated using an internal equation of state, which we develop here, and the temperatures of the external and internal DoF are coupled using a fluctuation-dissipation relation. The DPDE force expression requires specification of the input parameter σ that determines the rate at which energy is exchanged between external and internal DoF. We adjusted σ based on the predictions for relaxation processes obtained from MD simulations. The parameterized DPDE model was employed in large-scale simulations of shock compression of TATB. We show that the rate of energy exchange governed by σ can significantly influence the transient behavior of the system behind the shock.

  16. Characteristics of energy exchange between inter- and intramolecular degrees of freedom in crystalline 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) with implications for coarse-grained simulations of shock waves in polyatomic molecular crystals

    International Nuclear Information System (INIS)

    Kroonblawd, Matthew P.; Sewell, Thomas D.; Maillet, Jean-Bernard

    2016-01-01

    In this report, we characterize the kinetics and dynamics of energy exchange between intramolecular and intermolecular degrees of freedom (DoF) in crystalline 1,3,5-triamino-2,4,6-trinitrobenzene (TATB). All-atom molecular dynamics (MD) simulations are used to obtain predictions for relaxation from certain limiting initial distributions of energy between the intra- and intermolecular DoF. The results are used to parameterize a coarse-grained Dissipative Particle Dynamics at constant Energy (DPDE) model for TATB. Each TATB molecule in the DPDE model is represented as an all-atom, rigid-molecule mesoparticle, with explicit external (molecular translational and rotational) DoF and coarse-grained implicit internal (vibrational) DoF. In addition to conserving linear and angular momentum, the DPDE equations of motion conserve the total system energy provided that particles can exchange energy between their external and internal DoF. The internal temperature of a TATB molecule is calculated using an internal equation of state, which we develop here, and the temperatures of the external and internal DoF are coupled using a fluctuation-dissipation relation. The DPDE force expression requires specification of the input parameter σ that determines the rate at which energy is exchanged between external and internal DoF. We adjusted σ based on the predictions for relaxation processes obtained from MD simulations. The parameterized DPDE model was employed in large-scale simulations of shock compression of TATB. We show that the rate of energy exchange governed by σ can significantly influence the transient behavior of the system behind the shock

  17. Characteristics of energy exchange between inter- and intramolecular degrees of freedom in crystalline 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) with implications for coarse-grained simulations of shock waves in polyatomic molecular crystals

    Science.gov (United States)

    Kroonblawd, Matthew P.; Sewell, Thomas D.; Maillet, Jean-Bernard

    2016-02-01

    In this report, we characterize the kinetics and dynamics of energy exchange between intramolecular and intermolecular degrees of freedom (DoF) in crystalline 1,3,5-triamino-2,4,6-trinitrobenzene (TATB). All-atom molecular dynamics (MD) simulations are used to obtain predictions for relaxation from certain limiting initial distributions of energy between the intra- and intermolecular DoF. The results are used to parameterize a coarse-grained Dissipative Particle Dynamics at constant Energy (DPDE) model for TATB. Each TATB molecule in the DPDE model is represented as an all-atom, rigid-molecule mesoparticle, with explicit external (molecular translational and rotational) DoF and coarse-grained implicit internal (vibrational) DoF. In addition to conserving linear and angular momentum, the DPDE equations of motion conserve the total system energy provided that particles can exchange energy between their external and internal DoF. The internal temperature of a TATB molecule is calculated using an internal equation of state, which we develop here, and the temperatures of the external and internal DoF are coupled using a fluctuation-dissipation relation. The DPDE force expression requires specification of the input parameter σ that determines the rate at which energy is exchanged between external and internal DoF. We adjusted σ based on the predictions for relaxation processes obtained from MD simulations. The parameterized DPDE model was employed in large-scale simulations of shock compression of TATB. We show that the rate of energy exchange governed by σ can significantly influence the transient behavior of the system behind the shock.

  18. PREFACE: 19th International Conference on Electron Dynamics in Semiconductors, Optoelectronics and Nanostructures (EDISON'19)

    Science.gov (United States)

    González, T.; Martín-Martínez, M. J.; Mateos, J.

    2015-10-01

    The 19th International Conference on Electron Dynamics in Semiconductors, Optoelectronics and Nanostructures (EDISON'19) was held at the Hospedería Fonseca (Universidad de Salamanca, Spain), on 29 June - 2 July, 2015, and was organized by the Electronics Area from the University of Salamanca. The Conference is held biannually and covers the recent progress in the field of electron dynamics in solid-state materials and devices. This was the 19th meeting of the international conference series formerly named Hot Carriers in Semiconductors (HCIS), first held in Modena in 1973. In the edition of 1997 in Berlin the name of the conference changed to International Conference on Nonequilibrium Carrier Dynamics in Semiconductors, keeping the same acronym, HCIS; and finally in the edition of Montpellier in 2009 the name was again changed to the current one, International Conference on Electron Dynamics in Semiconductors, Optoelectronics and Nanostructures (EDISON). The latest editions took place in Santa Barbara, USA, in 2011 and Matsue, Japan, in 2013. Research work on electron dynamics involves quite different disciplines, and requires both fundamental and technological scientific efforts. Attendees to the conference come mostly from academic institutions, belonging to both theoretical and experimental groups working in a variety of fields, such as solid-state physics, electronics, optics, electrical engineering, material science, laser physics, etc. In this framework, events like the EDISON conference become a basic channel for the progress in the field. Here, researchers working in different areas can meet, present their latest advances and exchange their ideas. The program of EDISON'19 included 13 invited papers, 61 oral contributions and 73 posters. These contributions originated from scientists in more than 30 different countries. The Conference gathered 140 participants, coming from 24 different countries, most from Europe, but also with a significant participation

  19. Intramolecular telomeric G-quadruplexes dramatically inhibit DNA synthesis by replicative and translesion polymerases, revealing their potential to lead to genetic change.

    Directory of Open Access Journals (Sweden)

    Deanna N Edwards

    Full Text Available Recent research indicates that hundreds of thousands of G-rich sequences within the human genome have the potential to form secondary structures known as G-quadruplexes. Telomeric regions, consisting of long arrays of TTAGGG/AATCCC repeats, are among the most likely areas in which these structures might form. Since G-quadruplexes assemble from certain G-rich single-stranded sequences, they might arise when duplex DNA is unwound such as during replication. Coincidentally, these bulky structures when present in the DNA template might also hinder the action of DNA polymerases. In this study, single-stranded telomeric templates with the potential to form G-quadruplexes were examined for their effects on a variety of replicative and translesion DNA polymerases from humans and lower organisms. Our results demonstrate that single-stranded templates containing four telomeric GGG runs fold into intramolecular G-quadruplex structures. These intramolecular G quadruplexes are somewhat dynamic in nature and stabilized by increasing KCl concentrations and decreasing temperatures. Furthermore, the presence of these intramolecular G-quadruplexes in the template dramatically inhibits DNA synthesis by various DNA polymerases, including the human polymerase δ employed during lagging strand replication of G-rich telomeric strands and several human translesion DNA polymerases potentially recruited to sites of replication blockage. Notably, misincorporation of nucleotides is observed when certain translesion polymerases are employed on substrates containing intramolecular G-quadruplexes, as is extension of the resulting mismatched base pairs upon dynamic unfolding of this secondary structure. These findings reveal the potential for blockage of DNA replication and genetic changes related to sequences capable of forming intramolecular G-quadruplexes.

  20. Dynamic changes of intramural hematoma in patients with acute spontaneous internal carotid artery dissection.

    Science.gov (United States)

    Heldner, Mirjam R; Nedelcheva, Mila; Yan, Xin; Slotboom, Johannes; Mathier, Etienne; Hulliger, Justine; Verma, Rajeev K; Sturzenegger, Matthias; Jung, Simon; Bernasconi, Corrado; Arnold, Marcel; Wiest, Roland; Fischer, Urs

    2015-08-01

    We prospectively investigated temporal and spatial evolution of intramural hematomas in patients with acute spontaneous internal carotid artery dissection using repeated magnetic resonance imaging over six-months. The aim of the present study was to assess dynamic changes of intramural hematoma in patients with acute spontaneous internal carotid artery dissection at multiple follow-up time-points with T1w, PD/T2w, and magnetic resonance angiography. We performed serial multiparametric magnetic resonance imaging in 10 patients with spontaneous internal carotid artery dissection on admission, at days 1, 3, 7-14 and at months 1·5, 3, and 6. We calculated the volume and extension of the hyperintense intramural hematoma using T1w and PD/T2w fat suppressed sequences and assessed the degree of stenosis due to the hematoma using magnetic resonance angiography. Mean interval from symptom onset to first magnetic resonance imaging was two-days (SD 2·7). Two patients presented with ischemic stroke, three with transient ischemic attacks, and five with pain and local symptoms only. Nine patients had a transient increase of the intramural hematoma volume, mainly up to day 10 after symptom onset. Fifty percent had a transient increase in the degree of the internal carotid artery stenosis on MRA, one resulting in a temporary occlusion. Lesions older than one-week were predominantly characterized by a shift from iso- to hyperintese signal on T2w images. At three-month follow-up, intramural hematoma was no longer detectable in 80% of patients and had completely resolved in all patients after six-months. Spatial and temporal dynamics of intramural hematomas after spontaneous internal carotid artery dissection showed an early volume increase with concomitant progression of the internal carotid artery stenosis in 5 of 10 patients. Although spontaneous internal carotid artery dissection overall carries a good prognosis with spontaneous hematoma resorption in all our patients, early

  1. The Discursive Dynamics in Teacher Education: Authoritative Discourse or Internally Persuasive Discourse?

    Directory of Open Access Journals (Sweden)

    Maria Otilia Guimarães Ninin

    2014-06-01

    Full Text Available This article, based on the socio-cultural-historical theoretical perspective, discusses the activity in which individuals engage as constitutive of the social roles they occupy. It aims to trigger discussion of discursive dynamics in the context of critical-collaborative teacher education, focusing on internally persuasive and authoritative discourse (BAKHTIN, 1981 and their co-occurrence in situations of negotiation of meanings. This distinction is relevant because it is possible to understand different argumentative enunciations or not, conducted by educators in training, which approach or distance themselves from those cast by their trainers or isolated voices of theoretical practice, indicating possibilities of creation or reduction of dialogic expansion. From the emphasis on internally persuasive discourse, this article highlights the critical - collaborative argumentation role in training educators. Examples selected from a corpus of research collected in public school in São Paulo subsidize the discussion supported by Bakhtin (1981 and Vygotsky (1998; 2001.

  2. Dynamic response of a system with internal heat sources cooled by a flowing incompressible fluid

    International Nuclear Information System (INIS)

    Georgescu, R.; Dobrescu, C.

    1975-01-01

    The paper investigates the dynamic temperature response of an incompressible fluid which cools a duct with internal heat sources sinusoidally oscillated. The analytical results utilise the Laplace transformation technique. The experimental and calculated results are obtained by transfer function approach. Comparison of the calculated with the experimental data indicates agreement from 6 to 24 percent for the amplitude and up to 30 degree for the phase-shift. All the calculated data are below the experimental ones. The analytical method of transfer function approach presents interest and may be utilized for the initial calculations giving good results for flow rates above 1000 kg per hour

  3. Analysis of the fluid-structure dynamic interaction of reactor pressure vessel internals during blowdown

    International Nuclear Information System (INIS)

    Schlechtendahl, E.G.; Krieg, R.; Schumann, U.

    1977-01-01

    The loadings on reactor internal structures (in particular the core barrel) induced during a PWR-blowdown must not result in excessive stresses and strains. The deformations are strongly influenced by the coupling of fluid and structure dynamics and it is necessary, therefore, to develop and apply new coupled analysis tools. In this paper a survey is given over work currently in progress in the Nuclear Research Center Karlsruhe and the Los Alamos Scientific Laboratory which aim towards 'best estimate codes'. The new methods will be verified by means of the HDR-blowdown tests and other experiments. The results of several scoping calculations are presented and illustrated by movie films. (orig.) [de

  4. A Dynamic Programming Model for Internal Attack Detection in Wireless Sensor Networks

    Directory of Open Access Journals (Sweden)

    Qiong Shi

    2017-01-01

    Full Text Available Internal attack is a crucial security problem of WSN (wireless sensor network. In this paper, we focus on the internal attack detection which is an important way to locate attacks. We propose a state transition model, based on the continuous time Markov chain (CTMC, to study the behaviors of the sensors in a WSN under internal attack. Then we conduct the internal attack detection model as the epidemiological model. In this model, we explore the detection rate as the rate of a compromised state transition to a response state. By using the Bellman equation, the utility for the state transitions of a sensor can be written in standard forms of dynamic programming. It reveals a natural way to find the optimal detection rate that is by maximizing the total utility of the compromised state of the node (the sum of current utility and future utility. In particular, we encapsulate the current state, survivability, availability, and energy consumption of the WSN into an information set. We conduct extensive experiments and the results show the effectiveness of our solutions.

  5. Dynamic Thermodynamics with Internal Energy, Volume, and Amount of Moles as States : Application to Liquefied Gas Tank

    NARCIS (Netherlands)

    Arendsen, A. R. J.; Versteeg, G. F.

    2009-01-01

    Dynamic models for process design, optimization, and control usually solve a set of heat and/or mass balances as a function of time and/or position in the process. To obtain more robust dynamic models and to minimize the amount of assumptions, internal energy, volume, and amount of moles are chosen

  6. Intramolecular ketenimine-ketenimine [2 + 2] and [4 + 2] cycloadditions.

    Science.gov (United States)

    Alajarín, Mateo; Bonillo, Baltasar; Sanchez-Andrada, Pilar; Vidal, Angel; Bautista, Delia

    2007-07-20

    Bis(ketenimines), in which the two heterocumulenic functions are placed in close proximity on a carbon skeleton to allow their mutual interaction, show a rich and not easily predictable chemistry. Intramolecular [2 + 2] or [4 + 2] cycloadditions are, respectively, observed when both ketenimine functions are supported on either ortho-benzylic or 2,2'-biphenylenic scaffolds. In addition, nitrogen-to-carbon [1,3] and [1,5] shifts of arylmethyl groups in N-arylmethyl-C,C-diphenyl ketenimines are also disclosed.

  7. Intramolecular photoinduced electron-transfer in azobenzene-perylene diimide

    International Nuclear Information System (INIS)

    Feng Wen-Ke; Wang Shu-Feng; Gong Qi-Huang; Feng Yi-Yu; Feng Wei; Yi Wen-Hui

    2010-01-01

    This paper studies the intramolecular photoinduced electron-transfer (PET) of covalent bonded azobenzene-perylene diimide (AZO-PDI) in solvents by using steady-state and time-resolved fluorescence spectroscopy together with ultrafast transient absorption spectroscopic techniques. Fast fluorescence quenching is observed when AZO-PDI is excited at characteristic wavelengths of AZO and perylene moieties. Reductive electron-transfer with transfer rate faster than 10 11 s −1 is found. This PET process is also consolidated by femtosecond transient absorption spectra

  8. Synthesis of anatoxin a via intramolecular cyclization of iminium salts

    International Nuclear Information System (INIS)

    Bates, H.A.; Rapoport, H.

    1979-01-01

    Anatoxin a (1) has been synthesized by exploiting intramolecular cyclization between an iminium salt and a nucleophilic carbon to construct the 9-azabicyclo[4.2.1]nonane ring system. Cyclization of malonate iminiumsalt 16 at alkaline pH afforded a low yield of bicyclic malonate 18 owing to an unfavorable equilibrium constant and lability of the iminium salt in base. In contrast, cyclization of ketoiminium salt 31 afforded a good yield of bicyclic ketone 34 in acidic methanol. Dihydropyrrolium salts 16 and 31 were generated quantitatively by decarbonylation of substituted N-methylprolines 15 and 30b, obtained by reduction of the corresponding pyrroles

  9. Intramolecular Hydrogen Bonding in (2-Hydroxybenzoyl)benzoylmethane Enol

    DEFF Research Database (Denmark)

    Hansen, Bjarke Knud Vilster; Winther, Morten; Spanget-Larsen, Jens

    2014-01-01

    , and the dienol form of 1,3-dibenzoylacetone. But in these examples the two H-bonds are equivalent, while in the case of OHDBM they are chemically different, involving one enolic and one phenolic hydroxy group. OHDBM is thus an interesting model compound with two competing H-bonds to the same carbonyl group......In the stable enol tautomer of the title compound (OHDBM), one carbonyl group is flanked by two β-hydroxy groups, giving rise to bifold intramolecular H-bonding. A similar situation is found in other β,β'-dihydroxy carbonyl compounds like chrysazin, anthralin, 2,2'-dihydroxybenzophenone...

  10. International and Domestic Business Cycles as Dynamics of a Network of Networks

    Science.gov (United States)

    Ikeda, Yuichi; Iyetomi, Hiroshi; Aoyama, Hideaki; Yoshikawa, Hiroshi

    2014-03-01

    Synchronization in business cycles has attracted economists and physicists as self-organization in the time domain. From a different point of view, international and domestic business cycles are also interesting as dynamics of a network of networks or a multi-level network. In this paper, we analyze the Indices of Industrial Production monthly time-series in Japan from January 1988 to December 2007 to develop a deeper understanding of domestic business cycles. The frequency entrainment and the partial phase locking were observed for the 16 sectors to be direct evidence of synchronization. We also showed that the information of the economic shock is carried by the phase time-series. The common shock and individual shocks are separated using phase time-series. The former dominates the economic recession in all of 1992, 1998 and 2001. In addition to the above analysis, we analyze the quarterly GDP time series for Australia, Canada, France, Italy, the United Kingdom, and the United States from Q2 1960 to Q1 2010 in order to clarify its origin. We find frequency entrainment and partial phase locking. Furthermore, a coupled limit-cycle oscillator model is developed to explain the mechanism of synchronization. In this model, the interaction due to international trade is interpreted as the origin of the synchronization. The obtained results suggest that the business cycle may be described as a dynamics of the multi-level coupled oscillators exposed to random individual shocks.

  11. Smooth Adaptive Internal Model Control Based on U Model for Nonlinear Systems with Dynamic Uncertainties

    Directory of Open Access Journals (Sweden)

    Li Zhao

    2016-01-01

    Full Text Available An improved smooth adaptive internal model control based on U model control method is presented to simplify modeling structure and parameter identification for a class of uncertain dynamic systems with unknown model parameters and bounded external disturbances. Differing from traditional adaptive methods, the proposed controller can simplify the identification of time-varying parameters in presence of bounded external disturbances. Combining the small gain theorem and the virtual equivalent system theory, learning rate of smooth adaptive internal model controller has been analyzed and the closed-loop virtual equivalent system based on discrete U model has been constructed as well. The convergence of this virtual equivalent system is proved, which further shows the convergence of the complex closed-loop discrete U model system. Finally, simulation and experimental results on a typical nonlinear dynamic system verified the feasibility of the proposed algorithm. The proposed method is shown to have lighter identification burden and higher control accuracy than the traditional adaptive controller.

  12. Internal exposure dynamics drive the Adverse Outcome Pathways of synthetic glucocorticoids in fish

    Science.gov (United States)

    Margiotta-Casaluci, Luigi; Owen, Stewart F.; Huerta, Belinda; Rodríguez-Mozaz, Sara; Kugathas, Subramanian; Barceló, Damià; Rand-Weaver, Mariann; Sumpter, John P.

    2016-02-01

    The Adverse Outcome Pathway (AOP) framework represents a valuable conceptual tool to systematically integrate existing toxicological knowledge from a mechanistic perspective to facilitate predictions of chemical-induced effects across species. However, its application for decision-making requires the transition from qualitative to quantitative AOP (qAOP). Here we used a fish model and the synthetic glucocorticoid beclomethasone dipropionate (BDP) to investigate the role of chemical-specific properties, pharmacokinetics, and internal exposure dynamics in the development of qAOPs. We generated a qAOP network based on drug plasma concentrations and focused on immunodepression, skin androgenisation, disruption of gluconeogenesis and reproductive performance. We showed that internal exposure dynamics and chemical-specific properties influence the development of qAOPs and their predictive power. Comparing the effects of two different glucocorticoids, we highlight how relatively similar in vitro hazard-based indicators can lead to different in vivo risk. This discrepancy can be predicted by their different uptake potential, pharmacokinetic (PK) and pharmacodynamic (PD) profiles. We recommend that the development phase of qAOPs should include the application of species-species uptake and physiologically-based PK/PD models. This integration will significantly enhance the predictive power, enabling a more accurate assessment of the risk and the reliable transferability of qAOPs across chemicals.

  13. Intramolecular energy transfer and mode-specific effects in unimolecular reactions of 1,2-difluoroethane

    Science.gov (United States)

    Raff, Lionel M.

    1989-06-01

    The unimolecular decomposition reactions of 1,2-difluoroethane upon mode-specific excitation to a total internal energy of 7.5 eV are investigated using classical trajectory methods and a previously formulated empirical potential-energy surface. The decomposition channels for 1,2-difluoroethane are, in order of importance, four-center HF elimination, C-C bond rupture, and hydrogen-atom dissociation. This order is found to be independent of the particular vibrational mode excited. Neither fluorine-atom nor F2 elimination reactions are ever observed even though these dissociation channels are energetically open. For four-center HF elimination, the average fraction of the total energy partitioned into internal HF motion varies between 0.115-0.181 depending upon the particular vibrational mode initially excited. The internal energy of the fluoroethylene product lies in the range 0.716-0.776. Comparison of the present results with those previously obtained for a random distribution of the initial 1,2-difluoroethane internal energy [J. Phys. Chem. 92, 5111 (1988)], shows that numerous mode-specific effects are present in these reactions in spite of the fact that intramolecular energy transfer rates for this system are 5.88-25.5 times faster than any of the unimolecular reaction rates. Mode-specific excitation always leads to a total decomposition rate significantly larger than that obtained for a random distribution of the internal energy. Excitation of different 1,2-difluoroethane vibrational modes is found to produce as much as a 51% change in the total decomposition rate. Mode-specific effects are also seen in the product energy partitioning. The rate coefficients for decomposition into the various channels are very sensitive to the particular mode excited. A comparison of the calculated mode-specific effects with the previously determined mode-to-mode energy transfer rate coefficients [J. Chem. Phys. 89, 5680 (1988)] shows that, to some extent, the presence of mode

  14. Separation Dynamics of Controlled Internal Flow in an Adverse Pressure Gradient

    Science.gov (United States)

    Peterson, C. J.; Vukasinovic, B.; Glezer, A.

    2017-11-01

    The effects of fluidic actuation on the dynamic evolution of aggressive internal flow separation is investigated at speeds up to M = 0.4 within a constant-width diffuser branching off of a primary flow duct. It is shown that a spanwise array of fluidic actuators upstream of the separation actively controls the flow constriction (and losses) within the diffuser and consequently the local pressure gradient at its entrance. The effectiveness of the actuation, as may be measured by the increased flow rate that is diverted through the diffuser, scales with its flow rate coefficient. In the presence of actuation (0.7% mass fraction), the mass flow rate in the primary duct increases by 10% while the fraction of the diverted mass flow rate in the diffuser increases by more than 45%. The flow dynamics near separation in the absence and presence of actuation are characterized using high speed particle image velocimetry and analyzed using proper orthogonal and spectral decompositions. In particular, the spectral contents of the incipient boundary layer separation are compared in the absence and presence of actuation with emphasis on the changes in local dynamics near separation as the characteristic cross stream scale of the boundary layer increases with separation delay.

  15. Internal models of limb dynamics and the encoding of limb state

    Science.gov (United States)

    Hwang, Eun Jung; Shadmehr, Reza

    2005-09-01

    Studies of reaching suggest that humans adapt to novel arm dynamics by building internal models that transform planned sensory states of the limb, e.g., desired limb position and its derivatives, into motor commands, e.g., joint torques. Earlier work modeled this computation via a population of basis elements and used system identification techniques to estimate the tuning properties of the bases from the patterns of generalization. Here we hypothesized that the neural representation of planned sensory states in the internal model might resemble the signals from the peripheral sensors. These sensors normally encode the limb's actual sensory state in which movement errors occurred. We developed a set of equations based on properties of muscle spindles that estimated spindle discharge as a function of the limb's state during reaching and drawing of circles. We then implemented a simulation of a two-link arm that learned to move in various force fields using these spindle-like bases. The system produced a pattern of adaptation and generalization that accounted for a wide range of previously reported behavioral results. In particular, the bases showed gain-field interactions between encoding of limb position and velocity, very similar to the gain fields inferred from behavioral studies. The poor sensitivity of the bases to limb acceleration predicted behavioral results that were confirmed by experiment. We suggest that the internal model of limb dynamics is computed by the brain with neurons that encode the state of the limb in a manner similar to that expected of muscle spindle afferents.

  16. Examining the Dynamic Structure of Daily Internalizing and Externalizing Behavior at Multiple Levels of Analysis

    Directory of Open Access Journals (Sweden)

    Aidan G.C. Wright

    2015-12-01

    Full Text Available Psychiatric diagnostic covariation suggests that the underlying structure of psychopathology is not one of circumscribed disorders. Quantitative modeling of individual differences in diagnostic patterns has uncovered several broad domains of mental disorder liability, of which the Internalizing and Externalizing spectra have garnered the greatest support. These dimensions have generally been estimated from lifetime or past-year comorbidity patters, which are distal from the covariation of symptoms and maladaptive behavior that ebb and flow in daily life. In this study, structural models are applied to daily diary data (Median = 94 days of maladaptive behaviors collected from a sample (N = 101 of individuals diagnosed with personality disorders. Using multilevel and unified structural equation modeling, between-person, within-person, and person-specific structures were estimated from 16 behaviors that are encompassed by the Internalizing and Externalizing spectra. At the between-person level (i.e., individual differences in average endorsement across days we found support for a two-factor Internalizing-Externalizing model, which exhibits significant associations with corresponding diagnostic spectra. At the within-person level (i.e., dynamic covariation among daily behavior pooled across individuals we found support for a more differentiated, four-factor, Negative Affect-Detachment-Hostility-Impulsivity structure. Finally, we demonstrate that the person-specific structures of associations between these four domains are highly idiosyncratic.

  17. Heterocycles by Transition Metals Catalyzed Intramolecular Cyclization of Acetylene Compounds

    International Nuclear Information System (INIS)

    Vizer, S.A.; Yerzhanov, K.B.; Dedeshko, E.C.

    2003-01-01

    Review shows the new strategies in the synthesis of heterocycles, having nitrogen, oxygen and sulfur atoms, via transition metals catalyzed intramolecular cyclization of acetylenic compounds on the data published at the last 30 years, Unsaturated heterocyclic compounds (pyrroles and pyrroline, furans, dihydro furans and benzofurans, indoles and iso-indoles, isoquinolines and isoquinolinones, aurones, iso coumarins and oxazolinone, lactams and lactones with various substitutes in heterocycles) are formed by transition metals, those salts [PdCl 2 , Pd(OAc) 2 , HgCl 2 , Hg(OAc) 2 , Hg(OCOCF 3 ) 2 , AuCl 3 ·2H 2 O, NaAuCl 4 ·2H 2 O, CuI, CuCl], oxides (HgO) and complexes [Pd(OAc) 2 (PPh 3 )2, Pd(PPh 3 ) 4 , PdCl 2 (MeCN) 2 , Pd(OAc ) 2 /TPPTS] catalyzed intramolecular cyclization of acetylenic amines, amides, ethers, alcohols, acids, ketones and βdiketones. More complex hetero polycyclic systems typical for natural alkaloids can to obtain similar. Proposed mechanisms of pyrroles, isoquinolines, iso indoles and indoles, benzofurans and iso coumarins, thiazolopyrimidinones formation are considered. (author)

  18. Estimating Rheological Parameters of Anhydrite from Folded Evaporite sequences: Implications for Internal Dynamics of Salt Structure

    Science.gov (United States)

    Adamuszek, Marta; Dabrowski, Marcin; Schmalholz, Stefan M.; Urai, Janos L.; Raith, Alexander

    2015-04-01

    Salt structures have been identified as a potential target for hydrocarbon, CO2, or radioactive waste storage. The most suitable locations for magazines are considered in the thick and relatively homogeneous rock salt layers. However, salt structures often consist of the evaporite sequence including rock salt intercalated with other rock types e.g.: anhydrite, gypsum, potassium and magnesium salt, calcite, dolomite, or shale. The presence of such heterogeneities causes a serious disturbance in the structure management. Detailed analysis of the internal architecture and internal dynamics of the salt structure are crucial for evaluating them as suitable repositories and also their long-term stability. The goal of this study is to analyse the influence of the presence of anhydrite layers on the internal dynamics of salt structures. Anhydrite is a common rock in evaporite sequences. Its physical and mechanical properties strongly differ from the properties of rock salt. The density of anhydrite is much higher than the density of salt, thus anhydrite is likely to sink in salt causing the disturbance of the surrounding structures. This suggestion was the starting point to the discussion about the long-term stability of the magazines in salt structures [1]. However, the other important parameter that has to be taken into account is the viscosity of anhydrite. The high viscosity ratio between salt and anhydrite can restrain the layer from sinking. The rheological behaviour of anhydrite has been studied in laboratory experiments [2], but the results only provide information about the short-term behaviour. The long-term behaviour can be best predicted using indirect methods e.g. based on the analysis of natural structures that developed over geological time scale. One of the most promising are fold structures, the shape of which is very sensitive to the rheological parameters of the deforming materials. Folds can develop in mechanically stratified materials during layer

  19. International Collaboration and Spatial Dynamics of US Patenting in Central and Eastern Europe 1981-2010

    Science.gov (United States)

    Lengyel, Balázs; Leskó, Mariann

    2016-01-01

    How did post-socialist transition and a parallel shift in international labor division restructure regional innovation systems in Central and Eastern Europe? This question is increasingly important, because current EU innovation policy is combined with regional development in Smart Specialization Strategies; however, spatial trends of innovation in Central and Eastern Europe are not fully understood which might lead to less than perfectly efficient policy. In this paper we describe the spatial dynamics of inventor activity in the Czech Republic, Hungary, Poland and Slovakia between 1981 and 2010 –a period that covers both the late socialist era and the post-socialist transition. Cleaning and analyzing the publicly available data from the United States Patent and Trademark Office we illustrate that Central and Eastern European patents made in international co-operations with partners outside the region receive more citations than those Central and Eastern European patents that lack international co-operation. Furthermore, the technological portfolio of the former patents has become increasingly independent from the technological portfolio of the latter class. A town-level analysis of the applicant-inventor ties reveals that inventors have started to work for foreign assignees in those towns where no innovation activity had been recorded before. However, the positive effect does not last long and patenting seems to be only periodic in the majority of these towns. Therefore, innovation policy in Central and Eastern European countries, as well as in other less developed regions, shall foster synergies between international and domestic collaborations in order to decrease regional disparities in patenting. PMID:27846288

  20. International Collaboration and Spatial Dynamics of US Patenting in Central and Eastern Europe 1981-2010.

    Science.gov (United States)

    Lengyel, Balázs; Leskó, Mariann

    2016-01-01

    How did post-socialist transition and a parallel shift in international labor division restructure regional innovation systems in Central and Eastern Europe? This question is increasingly important, because current EU innovation policy is combined with regional development in Smart Specialization Strategies; however, spatial trends of innovation in Central and Eastern Europe are not fully understood which might lead to less than perfectly efficient policy. In this paper we describe the spatial dynamics of inventor activity in the Czech Republic, Hungary, Poland and Slovakia between 1981 and 2010 -a period that covers both the late socialist era and the post-socialist transition. Cleaning and analyzing the publicly available data from the United States Patent and Trademark Office we illustrate that Central and Eastern European patents made in international co-operations with partners outside the region receive more citations than those Central and Eastern European patents that lack international co-operation. Furthermore, the technological portfolio of the former patents has become increasingly independent from the technological portfolio of the latter class. A town-level analysis of the applicant-inventor ties reveals that inventors have started to work for foreign assignees in those towns where no innovation activity had been recorded before. However, the positive effect does not last long and patenting seems to be only periodic in the majority of these towns. Therefore, innovation policy in Central and Eastern European countries, as well as in other less developed regions, shall foster synergies between international and domestic collaborations in order to decrease regional disparities in patenting.

  1. Spinal motor control system incorporates an internal model of limb dynamics.

    Science.gov (United States)

    Shimansky, Y P

    2000-10-01

    The existence and utilization of an internal representation of the controlled object is one of the most important features of the functioning of neural motor control systems. This study demonstrates that this property already exists at the level of the spinal motor control system (SMCS), which is capable of generating motor patterns for reflex rhythmic movements, such as locomotion and scratching, without the aid of the peripheral afferent feedback, but substantially modifies the generated activity in response to peripheral afferent stimuli. The SMCS is presented as an optimal control system whose optimality requires that it incorporate an internal model (IM) of the controlled object's dynamics. A novel functional mechanism for the integration of peripheral sensory signals with the corresponding predictive output from the IM, the summation of information precision (SIP) is proposed. In contrast to other models in which the correction of the internal representation of the controlled object's state is based on the calculation of a mismatch between the internal and external information sources, the SIP mechanism merges the information from these sources in order to optimize the precision of the controlled object's state estimate. It is demonstrated, based on scratching in decerebrate cats as an example of the spinal control of goal-directed movements, that the results of computer modeling agree with the experimental observations related to the SMCS's reactions to phasic and tonic peripheral afferent stimuli. It is also shown that the functional requirements imposed by the mathematical model of the SMCS comply with the current knowledge about the related properties of spinal neuronal circuitry. The crucial role of the spinal presynaptic inhibition mechanism in the neuronal implementation of SIP is elucidated. Important differences between the IM and a state predictor employed for compensating for a neural reflex time delay are discussed.

  2. Book of abstracts of International Conference on Nuclear Structure and Dynamics 2009

    International Nuclear Information System (INIS)

    Prepolec, L.; Niksic, T.

    2009-01-01

    Following the long tradition of nuclear physics conferences organized by our two institutes, e.g. the Adriatic International Conference and Europhysics Study Conferences, this meeting will provide a broad discussion forum on recent experimental and theoretical advances in the physics of nuclear structure and reactions. The main focus will be on the following topics: Nuclear structure and reactions far from stability; Exotic modes of excitation and decays; Collective phenomena and symmetries; Ab initio, cluster model, and shell-model approaches; Nuclear energy density functionals; Heavy-ion reactions at near-barrier energies; Dynamics of light-ion reactions; Nuclear reactions of astrophysical interest; Weak-interaction processes. This booklet contains the abstracts of contributions which will be presented at the Conference, either as invited and contributed talks, or oral poster presentations

  3. Recombination dynamics and internal quantum efficiency in InGaN

    International Nuclear Information System (INIS)

    Murotani, Hideaki; Andoh, Hiroya; Tsukamoto, Takehiko; Sugiura, Toko; Yamada, Yoichi; Tabata, Takuya; Honda, Yoshio; Yamaguchi, Masahito; Amano, Hiroshi

    2014-01-01

    Recombination dynamics and internal quantum efficiency (IQE) of green luminescent InGaN nanowires with different crystalline qualities have been studied by means photoluminescence (PL) and time-resolved PL spectroscopy. Temperature- and excitation-power-density-dependent PL spectroscopy enabled to evaluate the IQE as a function of excitation power density. The shape of the efficiency curves at low temperature strongly depended on the magnitude of nonradiative recombination processes. This leads to the misestimation of the IQE in the lower quality nanowire. In addition, the PL decay curves were well described by a double exponential function both at 6 and 300 K. The PL decay time of the faster component was affected by nonradiative recombination processes even at low temperature. This indicated that the radiative recombination lifetime cannot be estimated from the PL decay time in the lower quality nanowire. (copyright 2014 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  4. THE IMPACT OF THE ECONOMIC CRISIS ON THE DYNAMIC OF INTERNATIONAL FDI

    Directory of Open Access Journals (Sweden)

    Lenuţa Carp

    2012-03-01

    Full Text Available FDI flows are internationally recognized for the benefits they generate (technological transfer, know – how, industrial reorganization, raising the number of working places. Foreign capitals increased significantly under the impact of globalization and accelerated the interdependencies between economies up to 2007, but, in the current crisis, the dynamic of FDI flows was affected in a negative manner, both in developed economies and in the developing ones. The aim of this paper is to reveal and analyze the evolution of FDI flows in the period 2007 – 2010, emphasizing the strong impact that economic crisis exerts. The results of the analysis presents the descending trend up to 2009, since 2010 being noticed a slight recovery which continued in the first trimester of 2011 and according to the forecasts will continue in the future.

  5. Influence of an Internally-Generated QBO on Modeled Stratospheric Dynamics and Ozone

    Science.gov (United States)

    Hurwitz, M. M.; Newman, P. A.; Song, I. S.

    2011-01-01

    A GEOS V2 CCM simulation with an internally generated quasi-biennial oscillation (QBO) signal is compared to an otherwise identical simulation without a QBO. In a present-day climate, inclusion of the modeled QBO makes a significant difference to stratospheric dynamics and ozone throughout the year. The QBO enhances variability in the tropics, as expected, but also in the polar stratosphere in some seasons. The modeled QBO also affects the mean stratospheric climate. Because tropical zonal winds in the baseline simulation are generally easterly, there is a relative increase in zonal wind magnitudes in tropical lower and middle stratosphere in the QBO simulation. Extra-tropical differences between the QBO and 'no QBO' simulations thus reflect a bias toward the westerly phase of the QBO: a relative strengthening and poleward shifting the polar stratospheric jets, and a reduction in Arctic lower stratospheric ozone.

  6. Internal friction studies on dynamic strain aging in P91 ferritic steel

    International Nuclear Information System (INIS)

    Zhou, Hongwei; Fang, Junfei; Chen, Yan; Yang, Lei; Zhang, Hui; Lu, Yun; He, Yizhu

    2016-01-01

    The temperature of dynamic strain aging (DSA) regime in P91 steel is between 523 K and 773 K. The activation energy (Q) for onset of DSA is 73 kJ/mol, while that for finale of DSA is 202 kJ/mol. Two main Internal friction (IF) speaks were observed, Snoek and SKK with the activation energy of 67.9 kJ/mol and 121 kJ/mol, respectively. IF shows that activation energy of 73 kJ/mol is equal to that of C atom body diffusion in α-Fe, and 202 kJ/mol is equal to binding energy between C atoms and moving dislocations. These results confirm that the mechanism of DSA can be explained by the diffusion of C atoms and pinning between C and moving dislocation. These investigations indicate that DSA in P91 steel is resulted from C atom diffusion, instead of Cr or Mo atoms.

  7. A dynamic mathematical test of international property securities bubbles and crashes

    Science.gov (United States)

    Hui, Eddie C. M.; Zheng, Xian; Wang, Hui

    2010-04-01

    This study investigates property securities bubbles and crashes by using a dynamic mathematical methodology developed from the previous research (Watanabe et al. 2007a, b [31,32]). The improved model is used to detect the bubble and crash periods in five international countries/cities (namely, United States, United Kingdom, Japan, Hong Kong and Singapore) from Jan, 2000 to Oct, 2008. By this model definition, we are able to detect the beginning of each bubble period even before it bursts. Meanwhile, the empirical results show that most of property securities markets experienced bubble periods between 2003 and 2007, and crashes happened in Apr 2008 triggered by the Subprime Mortgage Crisis of US. In contrast, Japan suffered the shortest bubble period and no evidence has documented the existence of crash there.

  8. INTERNAL DYNAMICS WITHIN HADHRAMI ARABS IN INDONESIA: From Social Hierarchy to Islamic Doctrine

    Directory of Open Access Journals (Sweden)

    Syamsul Rijal

    2017-07-01

    Full Text Available This paper examines the current landscape of Hadhrami Arab Community in Indonesia. It aims to understand the internal fissures that affect the cohesion within the community. Some scholars contended that the conflicts taking place within the Hadhrami community are due to the Yemeni traditional stratification and nationalist orientation during colonial era. However, they do not include in their analysis the contemporary state of Hadhramis in Indonesia. This paper focuses on the contemporary era and argues that doctrinal contest and competition for religious authority have dominated the dynamics of conflict within Indonesian Hadhrami community. The paper will touch on the debates on the notion of Shi’ism among the so-called sayyids and Salafism among the followers of Al-Irsyad Al-Islamiyyah. It suggests that it is through these two currents of thought that the Hadhrami community in Indonesia not only exercise their power and authority, but also shape and transform their very identity.

  9. Computational fluid dynamics applied to flows in an internal combustion engine

    Science.gov (United States)

    Griffin, M. D.; Diwakar, R.; Anderson, J. D., Jr.; Jones, E.

    1978-01-01

    The reported investigation is a continuation of studies conducted by Diwakar et al. (1976) and Griffin et al. (1976), who reported the first computational fluid dynamic results for the two-dimensional flowfield for all four strokes of a reciprocating internal combustion (IC) engine cycle. An analysis of rectangular and cylindrical three-dimensional engine models is performed. The working fluid is assumed to be inviscid air of constant specific heats. Calculations are carried out of a four-stroke IC engine flowfield wherein detailed finite-rate chemical combustion of a gasoline-air mixture is included. The calculations remain basically inviscid, except that in some instances thermal conduction is included to allow a more realistic model of the localized sparking of the mixture. All the results of the investigation are obtained by means of an explicity time-dependent finite-difference technique, using a high-speed digital computer.

  10. Internal air flow analysis of a bladeless micro aerial vehicle hemisphere body using computational fluid dynamic

    Energy Technology Data Exchange (ETDEWEB)

    Othman, M. N. K., E-mail: najibkhir86@gmail.com, E-mail: zuradzman@unimap.edu.my, E-mail: hazry@unimap.edu.my, E-mail: khairunizam@unimap.edu.my, E-mail: shahriman@unimap.edu.my, E-mail: s.yaacob@unimap.edu.my, E-mail: syedfaiz@unimap.edu.my, E-mail: abadal@unimap.edu.my; Zuradzman, M. Razlan, E-mail: najibkhir86@gmail.com, E-mail: zuradzman@unimap.edu.my, E-mail: hazry@unimap.edu.my, E-mail: khairunizam@unimap.edu.my, E-mail: shahriman@unimap.edu.my, E-mail: s.yaacob@unimap.edu.my, E-mail: syedfaiz@unimap.edu.my, E-mail: abadal@unimap.edu.my; Hazry, D., E-mail: najibkhir86@gmail.com, E-mail: zuradzman@unimap.edu.my, E-mail: hazry@unimap.edu.my, E-mail: khairunizam@unimap.edu.my, E-mail: shahriman@unimap.edu.my, E-mail: s.yaacob@unimap.edu.my, E-mail: syedfaiz@unimap.edu.my, E-mail: abadal@unimap.edu.my; Khairunizam, Wan, E-mail: najibkhir86@gmail.com, E-mail: zuradzman@unimap.edu.my, E-mail: hazry@unimap.edu.my, E-mail: khairunizam@unimap.edu.my, E-mail: shahriman@unimap.edu.my, E-mail: s.yaacob@unimap.edu.my, E-mail: syedfaiz@unimap.edu.my, E-mail: abadal@unimap.edu.my; Shahriman, A. B., E-mail: najibkhir86@gmail.com, E-mail: zuradzman@unimap.edu.my, E-mail: hazry@unimap.edu.my, E-mail: khairunizam@unimap.edu.my, E-mail: shahriman@unimap.edu.my, E-mail: s.yaacob@unimap.edu.my, E-mail: syedfaiz@unimap.edu.my, E-mail: abadal@unimap.edu.my; Yaacob, S., E-mail: najibkhir86@gmail.com, E-mail: zuradzman@unimap.edu.my, E-mail: hazry@unimap.edu.my, E-mail: khairunizam@unimap.edu.my, E-mail: shahriman@unimap.edu.my, E-mail: s.yaacob@unimap.edu.my, E-mail: syedfaiz@unimap.edu.my, E-mail: abadal@unimap.edu.my; Ahmed, S. Faiz, E-mail: najibkhir86@gmail.com, E-mail: zuradzman@unimap.edu.my, E-mail: hazry@unimap.edu.my, E-mail: khairunizam@unimap.edu.my, E-mail: shahriman@unimap.edu.my, E-mail: s.yaacob@unimap.edu.my, E-mail: syedfaiz@unimap.edu.my, E-mail: abadal@unimap.edu.my [Centre of Excellence for Unmanned Aerial Systems, Universiti Malaysia Perlis, 01000 Kangar, Perlis (Malaysia); and others

    2014-12-04

    This paper explain the analysis of internal air flow velocity of a bladeless vertical takeoff and landing (VTOL) Micro Aerial Vehicle (MAV) hemisphere body. In mechanical design, before produce a prototype model, several analyses should be done to ensure the product's effectiveness and efficiency. There are two types of analysis method can be done in mechanical design; mathematical modeling and computational fluid dynamic. In this analysis, I used computational fluid dynamic (CFD) by using SolidWorks Flow Simulation software. The idea came through to overcome the problem of ordinary quadrotor UAV which has larger size due to using four rotors and the propellers are exposed to environment. The bladeless MAV body is designed to protect all electronic parts, which means it can be used in rainy condition. It also has been made to increase the thrust produced by the ducted propeller compare to exposed propeller. From the analysis result, the air flow velocity at the ducted area increased to twice the inlet air. This means that the duct contribute to the increasing of air velocity.

  11. Internal air flow analysis of a bladeless micro aerial vehicle hemisphere body using computational fluid dynamic

    Science.gov (United States)

    Othman, M. N. K.; Zuradzman, M. Razlan; Hazry, D.; Khairunizam, Wan; Shahriman, A. B.; Yaacob, S.; Ahmed, S. Faiz; Hussain, Abadalsalam T.

    2014-12-01

    This paper explain the analysis of internal air flow velocity of a bladeless vertical takeoff and landing (VTOL) Micro Aerial Vehicle (MAV) hemisphere body. In mechanical design, before produce a prototype model, several analyses should be done to ensure the product's effectiveness and efficiency. There are two types of analysis method can be done in mechanical design; mathematical modeling and computational fluid dynamic. In this analysis, I used computational fluid dynamic (CFD) by using SolidWorks Flow Simulation software. The idea came through to overcome the problem of ordinary quadrotor UAV which has larger size due to using four rotors and the propellers are exposed to environment. The bladeless MAV body is designed to protect all electronic parts, which means it can be used in rainy condition. It also has been made to increase the thrust produced by the ducted propeller compare to exposed propeller. From the analysis result, the air flow velocity at the ducted area increased to twice the inlet air. This means that the duct contribute to the increasing of air velocity.

  12. Internal air flow analysis of a bladeless micro aerial vehicle hemisphere body using computational fluid dynamic

    International Nuclear Information System (INIS)

    Othman, M. N. K.; Zuradzman, M. Razlan; Hazry, D.; Khairunizam, Wan; Shahriman, A. B.; Yaacob, S.; Ahmed, S. Faiz

    2014-01-01

    This paper explain the analysis of internal air flow velocity of a bladeless vertical takeoff and landing (VTOL) Micro Aerial Vehicle (MAV) hemisphere body. In mechanical design, before produce a prototype model, several analyses should be done to ensure the product's effectiveness and efficiency. There are two types of analysis method can be done in mechanical design; mathematical modeling and computational fluid dynamic. In this analysis, I used computational fluid dynamic (CFD) by using SolidWorks Flow Simulation software. The idea came through to overcome the problem of ordinary quadrotor UAV which has larger size due to using four rotors and the propellers are exposed to environment. The bladeless MAV body is designed to protect all electronic parts, which means it can be used in rainy condition. It also has been made to increase the thrust produced by the ducted propeller compare to exposed propeller. From the analysis result, the air flow velocity at the ducted area increased to twice the inlet air. This means that the duct contribute to the increasing of air velocity

  13. International Conference on Computer Modelling of Seas and Coastal Regions and Boundary Elements and Fluid Dynamics

    CERN Document Server

    Partridge, P; Boundary Elements in Fluid Dynamics

    1992-01-01

    This book Boundary Elements in Fluid Dynamics is the second volume of the two volume proceedings of the International Conference on Computer Modelling of Seas and Coastal Regions and Boundary Elements and Fluid Dynamics, held in Southampton, U.K., in April 1992. The Boundary Element Method (BEM) is now fully established as an ac­ curate and successful technique for solving engineering problems in a wide range of fields. The success of the method is due to its advantages in data reduction, as only the boundary of the region is modelled. Thus moving boundaries may be more easily handled, which is not the case if domain methods are used. In addition, the method is easily able to model regions to extending to infinity. Fluid mechanics is traditionally one of the most challenging areas of engi­ neering, the simulation of fluid motion, particularly in three dimensions, is always a serious test for any numerical method, and is an area in which BEM analysis may be used taking full advantage of its special character...

  14. Predictable Internal Brain Dynamics in EEG and Its Relation to Conscious States

    Directory of Open Access Journals (Sweden)

    Jaewook eYoo

    2014-06-01

    Full Text Available Consciousness is a complex and multi-faceted phenomenon defying scientific explanation. Part of the reason why this is the case is due to its subjective nature. In our previous computational experiments, to avoid such a subjective trap, we took a strategy to investigate objective necessary conditions of consciousness. Our basic hypothesis was that predictive internal dynamics serves as such a condition. This is in line with theories of consciousness that treat retention (memory, protention (anticipation, and primary impression as the tripartite temporal structure of consciousness. To test our hypothesis, we analyzed publicly available sleep and awake electroencephalogram (EEG data. Our results show that EEG signals from awake or rapid eye movement (REM sleep states have more predictable dynamics compared to those from slow-wave sleep (SWS. Since awakeness and REM sleep are associated with conscious states and SWS with unconscious or less consciousness states, these results support our hypothesis. The results suggest an intricate relationship among prediction, consciousness, and time, with potential applications to time perception and neurorobotics.

  15. Dynamic Oil Consumption Measurement of Internal Combustion Engines using Laser Spectroscopy.

    Science.gov (United States)

    Sellmeier, Stefan; Alonso, Eduardo; Boesl, Ulrich

    2014-01-07

    A new approach has been developed to measure dynamic consumption of lubricant oil in an internal combustion engine. It is based on the already known technique where sulfur is used as a natural tracer of the engine oil. Since ejection of motor oil in gaseous form into the exhaust is by far the main source of engine oil consumption, detection of sulfur in the exhaust emission is a valuable way to measure engine oil consumption in a dynamic way. In earlier approaches, this is done by converting all sulfur containing chemical components into SO2 by thermal pyrolysis in a high temperature furnace at atmospheric pressure. The so-formed SO2 then is detected by broadband-UV-induced fluorescence or mass spectrometric methods. The challenge is to reach the necessary detection limit of 50 ppb. The new approach presented here includes sulfur conversion in a low-pressure discharge cell and laser-induced fluorescence with wavelength and fluorescence lifetime selection. A limit of detection down to 10 ppb at a temporal resolution in the time scale of few seconds is reached. Extensive, promising studies have been performed at a real engine test bench. Future developments of a compact, mobile device based on these improvements are discussed.

  16. Vestibular stimulation interferes with the dynamics of an internal representation of gravity.

    Science.gov (United States)

    De Sá Teixeira, Nuno Alexandre; Hecht, Heiko; Diaz Artiles, Ana; Seyedmadani, Kimia; Sherwood, David P; Young, Laurence R

    2017-11-01

    The remembered vanishing location of a moving target has been found to be displaced downward in the direction of gravity (representational gravity) and more so with increasing retention intervals, suggesting that the visual spatial updating recruits an internal model of gravity. Despite being consistently linked with gravity, few inquiries have been made about the role of vestibular information in these trends. Previous experiments with static tilting of observers' bodies suggest that under conflicting cues between the idiotropic vector and vestibular signals, the dynamic drift in memory is reduced to a constant displacement along the body's main axis. The present experiment aims to replicate and extend these outcomes while keeping the observers' bodies unchanged in relation to physical gravity by varying the gravito-inertial acceleration using a short-radius centrifuge. Observers were shown, while accelerated to varying degrees, targets moving along several directions and were required to indicate the perceived vanishing location after a variable interval. Increases of the gravito-inertial force (up to 1.4G), orthogonal to the idiotropic vector, did not affect the direction of representational gravity, but significantly disrupted its time course. The role and functioning of an internal model of gravity for spatial perception and orientation are discussed in light of the results.

  17. Internal and External Dynamics in Language: Evidence from Verb Regularity in a Historical Corpus of English

    Science.gov (United States)

    Cuskley, Christine F.; Pugliese, Martina; Castellano, Claudio; Colaiori, Francesca; Loreto, Vittorio; Tria, Francesca

    2014-01-01

    Human languages are rule governed, but almost invariably these rules have exceptions in the form of irregularities. Since rules in language are efficient and productive, the persistence of irregularity is an anomaly. How does irregularity linger in the face of internal (endogenous) and external (exogenous) pressures to conform to a rule? Here we address this problem by taking a detailed look at simple past tense verbs in the Corpus of Historical American English. The data show that the language is open, with many new verbs entering. At the same time, existing verbs might tend to regularize or irregularize as a consequence of internal dynamics, but overall, the amount of irregularity sustained by the language stays roughly constant over time. Despite continuous vocabulary growth, and presumably, an attendant increase in expressive power, there is no corresponding growth in irregularity. We analyze the set of irregulars, showing they may adhere to a set of minority rules, allowing for increased stability of irregularity over time. These findings contribute to the debate on how language systems become rule governed, and how and why they sustain exceptions to rules, providing insight into the interplay between the emergence and maintenance of rules and exceptions in language. PMID:25084006

  18. Examining the Dynamic Structure of Daily Internalizing and Externalizing Behavior at Multiple Levels of Analysis

    Science.gov (United States)

    Wright, Aidan G. C.; Beltz, Adriene M.; Gates, Kathleen M.; Molenaar, Peter C. M.; Simms, Leonard J.

    2015-01-01

    Psychiatric diagnostic covariation suggests that the underlying structure of psychopathology is not one of circumscribed disorders. Quantitative modeling of individual differences in diagnostic patterns has uncovered several broad domains of mental disorder liability, of which the Internalizing and Externalizing spectra have garnered the greatest support. These dimensions have generally been estimated from lifetime or past-year comorbidity patters, which are distal from the covariation of symptoms and maladaptive behavior that ebb and flow in daily life. In this study, structural models are applied to daily diary data (Median = 94 days) of maladaptive behaviors collected from a sample (N = 101) of individuals diagnosed with personality disorders (PDs). Using multilevel and unified structural equation modeling, between-person, within-person, and person-specific structures were estimated from 16 behaviors that are encompassed by the Internalizing and Externalizing spectra. At the between-person level (i.e., individual differences in average endorsement across days) we found support for a two-factor Internalizing–Externalizing model, which exhibits significant associations with corresponding diagnostic spectra. At the within-person level (i.e., dynamic covariation among daily behavior pooled across individuals) we found support for a more differentiated, four-factor, Negative Affect-Detachment-Hostility-Disinhibition structure. Finally, we demonstrate that the person-specific structures of associations between these four domains are highly idiosyncratic. PMID:26732546

  19. An abnormally slow proton transfer reaction in a simple HBO derivative due to ultrafast intramolecular-charge transfer events.

    Science.gov (United States)

    Alarcos, Noemí; Gutierrez, Mario; Liras, Marta; Sánchez, Félix; Douhal, Abderrazzak

    2015-07-07

    We report on the steady-state, picosecond and femtosecond time-resolved studies of a charge and proton transfer dye 6-amino-2-(2'-hydroxyphenyl)benzoxazole (6A-HBO) and its methylated derivative 6-amino-2-(2'-methoxyphenyl)benzoxazole (6A-MBO), in different solvents. With femtosecond resolution and comparison with the photobehaviour of 6A-MBO, we demonstrate for 6A-HBO in solution, the photoproduction of an intramolecular charge-transfer (ICT) process at S1 taking place in ∼140 fs or shorter, followed by solvent relaxation in the charge transferred species. The generated structure (syn-enol charge transfer conformer) experiences an excited-state intramolecular proton-transfer (ESIPT) reaction to produce a keto-type tautomer. This subsequent proton motion occurs in 1.2 ps (n-heptane), 14 ps (DCM) and 35 ps (MeOH). In MeOH, it is assisted by the solvent molecules and occurs through tunneling for which we got a large kinetic isotope effect (KIE) of about 13. For the 6A-DBO (deuterated sample in CD3OD) the global proton-transfer reaction takes place in 200 ps, showing a remarkable slow KIE regime. The slow ESIPT reaction in DCM (14 ps), not through tunnelling as it is not sensitive to OH/OD exchange, has however to overcome an energy barrier using intramolecular as well as solvent coordinates. The rich ESIPT dynamics of 6A-HBO in the used solutions is governed by an ICT reaction, triggered by the amino group, and it is solvent dependent. Thus, the charge injection to a 6A-HBO molecular frame makes the ICT species more stable, and the phenol group less acidic, slowing down the subsequent ESIPT reaction. Our findings bring new insights into the coupling between ICT and ESIPT reactions on the potential-energy surfaces of several barriers.

  20. The dynamics of hepcidin-ferroportin internalization and consequences of a novel ferroportin disease mutation.

    Science.gov (United States)

    Wallace, Daniel F; McDonald, Cameron J; Ostini, Lesa; Iser, David; Tuckfield, Annabel; Subramaniam, V Nathan

    2017-10-01

    The hepcidin-ferroportin axis underlies the pathophysiology of many iron-associated disorders and is a key target for the development of therapeutics for treating iron-associated disorders. The aims of this study were to investigate the dynamics of hepcidin-mediated ferroportin internalization and the consequences of a novel disease-causing mutation on ferroportin function. Specific reagents for ferroportin are limited; we developed and characterized antibodies against the largest extracellular loop of ferroportin and developed a novel cell-based assay for studying hepcidin-ferroportin function. We show that hepcidin-mediated ferroportin internalization is a rapid process and could be induced using low concentrations of hepcidin. Targeted next-generation sequencing utilizing an iron metabolism gene panel developed in our group identified a novel ferroportin p.D84E variant in a patient with iron overload. Wild-type and mutant ferroportin constructs were generated, transfected into HEK293 cells and analysed using an all-in-one flow-cytometry-based assay to study the effects on hepcidin-mediated internalization and iron transport. Consistent with the classical phenotype of ferroportin disease, the p.D84E mutation results in an inability to transport iron and hepcidin insensitivity. These results validate a recently proposed 3D-structural model of ferroportin and highlight the significance of this variant in the structure and function of ferroportin. Our novel ferroportin antibody and assay will be valuable tools for investigating the regulation of hepcidin/ferroportin function and the development of novel approaches for the therapeutic modulation of iron homeostasis. © 2017 Wiley Periodicals, Inc.

  1. Intra-molecular selectivity of muonium towards chlorinated aromatic compounds

    International Nuclear Information System (INIS)

    Venkateswaran, K.; Stadlbauer, J.M.; Laing, M.E.; Klugkist, J.; Chong, D.P.; Porter, G.B.; Walker, D.C.

    1994-01-01

    Muon resonance studies show that muonium atoms (Mu) in ethanol add selectively to certain C-sites of aromatic compounds containing -Cl and -OH substituents. The sites chosen seem to be those carrying the lowest electron density. This helps to characterize Mu as a nucleophile in addition reactions and, in this respect, Mu differs from ordinary H-atoms. The study shows no apparent inter-molecular selectivity between a pair of aromatic solutes in an equimolar mixture, but strong intra-molecular selectivity in an ether composed of those two aromatic rings. This difference between intra- and inter-molecular selectivity is interpreted as kinetic in origin - arising from the 'caging effect' of the solvent and peculiar to reactions close to the diffusion-controlled limit. (orig.)

  2. Vibrational spectroscopy and intramolecular energy transfer in isocyanic acid (HNCO)

    International Nuclear Information System (INIS)

    Coffey, M.J.; Berghout, H.L.; Woods, E. III; Crim, F.F.

    1999-01-01

    Room temperature photoacoustic spectra in the region of the first through the fourth overtones (2ν 1 to 5ν 1 ) and free-jet action spectra of the second through the fourth overtones (3ν 1 to 5ν 1 ) of the N - H stretching vibration permit analysis of the vibrational and rotational structure of HNCO. The analysis identifies the strong intramolecular couplings that control the early stages of intramolecular vibrational energy redistribution (IVR) and gives the interaction matrix elements between the zero-order N - H stretching states and the other zero-order states with which they interact. The experimentally determined couplings and zero-order state separations are consistent with ab initio calculations of East, Johnson, and Allen [J. Chem. Phys. 98, 1299 (1993)], and comparison with the calculation identifies the coupled states and likely interactions. The states most strongly coupled to the pure N - H stretching zero-order states are ones with a quantum of N - H stretching excitation (ν 1 ) replaced by different combinations of N - C - O asymmetric or symmetric stretching excitation (ν 2 or ν 3 ) and trans-bending excitation (ν 4 ). The two strongest couplings of the nν 1 state are to the states (n-1)ν 1 +ν 2 +ν 4 and (n-1)ν 1 +ν 3 +2ν 4 , and sequential couplings through a series of low order resonances potentially play a role. The analysis shows that if the pure N - H stretch zero-order state were excited, energy would initially flow out of that mode into the strongly coupled mode in 100 fs to 700 fs, depending on the level of initial excitation. copyright 1999 American Institute of Physics

  3. Internal migration of Canadian immigrants, 1993–2004: Evidence from the Survey of Labour and Income Dynamics

    OpenAIRE

    Karen M. King; K. Bruce Newbold

    2011-01-01

    Combining the 1993, 1996, and 1999 six-year panels of the Survey of Labour and Income Dynamics Master Files, the purpose of the paper is twofold. First, it examines the migration and distribution patterns of the foreign-born across Census Metropolitan Areas (CMAs). Second, it examines how internal migration modeling results may differ whether pre- and post-migration measures are used. Results suggest that internal migration of the foreign-born generally does not increase their dispersion acr...

  4. Assess the Intra-molecular Cavity in PAMAM Dendrimers by Small Angle Neutron Scattering

    International Nuclear Information System (INIS)

    Chen, Wei-Ren

    2008-01-01

    In this report, we present a contrast variation small angle neutron scattering (SANS) study of a series of neutral PAMAM dendrimer in aqueous solutions using three different generations (G4-6) at a concentration of about 10 mg/ml. Varying the solvent hydrogen-deuterium ratio, the scattering contributions from the water molecules and the constituent components of PAMAM dendrimer can be determined. Using an analytical model of the scattering cross section I(Q) incorporating the effect of water penetration, we have quantified the intra-molecular space of PAMAM dendrimer by evaluating the number of guest water molecules and we draw a direct comparison to computational predictions. As expected, the overall available internal cavity was seen to increase as a function of increasing dendrimer generation. However, the fraction of water accessible volume in the internal cavity of a dendrimer was found to remain invariant for the three generation PAMAM dendrimers studied in this report. We have also estimated the average water density inside a dendrimer, which is found to be higher than that of bulk water

  5. Attributing Asymmetric Productivity Responses to Internal Ecosystem Dynamics and External Drivers Using Probabilistic Models

    Science.gov (United States)

    Parolari, A.; Goulden, M.

    2017-12-01

    A major challenge to interpreting asymmetric changes in ecosystem productivity is the attribution of these changes to external climate forcing or to internal ecophysiological processes that respond to these drivers (e.g., photosynthesis response to drying soil). For example, positive asymmetry in productivity can result from either positive skewness in the distribution of annual rainfall amount or from negative curvature in the productivity response to annual rainfall. To analyze the relative influences of climate and ecosystem dynamics on both positive and negative asymmetry in multi-year ANPP experiments, we use a multi-scale coupled ecosystem water-carbon model to interpret field experimental results that span gradients of rainfall skewness and ANPP response curvature. The model integrates rainfall variability, soil moisture dynamics, and net carbon assimilation from the daily to inter-annual scales. From the underlying physical basis of the model, we compute the joint probability distribution of the minimum and maximum ANPP for an annual ANPP experiment of N years. The distribution is used to estimate the likelihood that either positive or negative asymmetry will be observed in an experiment, given the annual rainfall distribution and the ANPP response curve. We estimate the total asymmetry as the mode of this joint distribution and the relative contribution attributable to rainfall skewness as the mode for a linear ANPP response curve. Applied to data from several long-term ANPP experiments, we find that there is a wide range of observed ANPP asymmetry (positive and negative) and a spectrum of contributions from internal and external factors. We identify the soil water holding capacity relative to the mean rain event depth as a critical ecosystem characteristic that controls the non-linearity of the ANPP response and positive curvature at high rainfall. Further, the seasonal distribution of rainfall is shown to control the presence or absence of negative

  6. Intramolecular addition of benzylic radicals onto ketenimines. Synthesis of 2-alkylindoles.

    Science.gov (United States)

    Alajarín, Mateo; Vidal, Angel; Ortín, María-Mar

    2003-12-07

    The inter- and intramolecular addition of free radicals onto ketenimines is studied. All the attempts to add intermolecularly several silicon, oxygen or carbon centered radicals to N-(4-methylphenyl)-C,C-diphenyl ketenimine were unsuccessful. In contrast, the intramolecular addition of benzylic radicals, generated from xanthates, onto the central carbon of a ketenimine function with its N atom linked to the ortho position of the aromatic ring occurred under a variety of reaction conditions. These intramolecular cyclizations provide a novel radical-mediated synthesis of 2-alkylindoles.

  7. Three Levels of Push-Pull Dynamics among Chinese International Students' Decision to Study Abroad in the Canadian Context

    Science.gov (United States)

    Chen, Jun Mian

    2017-01-01

    The extant literature on student migration flows generally focus on the traditional push-pull factors of migration at the individual level. Such a tendency excludes the broader levels affecting international student mobility. This paper proposes a hybrid of three levels of push-pull dynamics (micro-individual decision-making, meso-academic…

  8. Study of intramolecular isotope heterogeneity of organic oxy acids in order to detect sophisticated wines and juice drinks

    Directory of Open Access Journals (Sweden)

    Kuzmina Helen

    2014-01-01

    Full Text Available According to International Code of Oenological Practices it is allowed to use acide L(+tartrique for wine acidification, while use of synthetic dihydroxysuccinic acid is forbidden. Today it is impossible to differentiate natural dihydroxysuccinic acid from synthetic one by standard techniques. Even by using very sensitive method of isotope mass spectrometry certain difficulties emerge because total isotope characteristics of carbon of dihydroxysuccinic acid of different nature have the same values. However, isotope characteristics of carbon of intramolecular structural groups of dihydroxysuccinic acid made of different raw materials differ significantly. This allows specifying the nature of dihydroxysuccinic acid that is used for making of wines and juice drinks. In Russia, scientific and research institute of beer brewing and wine-making industry carried out a work for studying isotope characteristics of intramolecular isotope heterogeneity of dihydroxysuccinic acid from different origins in order to identify wines and juice drinks. Isotope characteristics of organic oxy acids from different origins were studied including them obtained by synthetic way and numeric range of value δ13 C,‰ were specified. The obtained results allow performing identification tests of wines and juice drinks to find out the products that contain not specified additives as that allowed for its use in production process.

  9. Dynamics of a Pipeline under the Action of Internal Shock Pressure

    Science.gov (United States)

    Il'gamov, M. A.

    2017-11-01

    The static and dynamic bending of a pipeline in the vertical plane under the action of its own weight is considered with regard to the interaction of the internal pressure with the curvature of the axial line and the axisymmetric deformation. The pressure consists of a constant and timevarying parts and is assumed to be uniformly distributed over the entire span between the supports. The pipeline reaction to the stepwise increase in the pressure is analyzed in the case where it is possible to determine the exact solution of the problem. The initial stage of bending determined by the smallness of elastic forces as compared to the inertial forces is introduced into the consideration. At this stage, the solution is sought in the form of power series and the law of pressure variation can be arbitrary. This solution provides initial conditions for determining the further process. The duration of the inertial stage is compared with the times of sharp changes of the pressure and the shock waves in fluids. The structure parameters are determined in the case where the shock pressure is accepted only by the inertial forces in the pipeline.

  10. Modelling of the dynamical behaviour of LWR internals by homogeneization methods

    International Nuclear Information System (INIS)

    Brochard, D.; Lepareux, M.; Gibert, R.J.; Delaigue, D.; Planchard, J.

    1987-01-01

    The upper plenum of the internals of PWR, the steam generator bundle, the nuclear reactor core, may be schematically represented by a beam bundle immersed in a fluid. The dynamical study of such a system needs to take into account fluid structure interaction. A refined modelisation at the scale of the tubes can be used but leads to a very important size of problem difficult to solve even on the biggest computers. The homogeneization method allows to have an approximation of the fluid structure interaction for the global behaviour of the bundle. It consists in replacing the heterogeneous physical medium (tubes and fluid) by an equivalent homogeneous medium whose characteristics are determined from the resolution of a set of problems on the elementary cell. The aim of this paper is to present the main steps of the determination of this equivalent medium in the case of small displacements (acoustic behaviour of the fluid) and in using displacement variables for both fluid and tubes. Then some precisions about the implementation of this method in computer codes will be given. (orig.)

  11. Intramolecular interactions in a new tris-dithizonatocobalt(III) complex

    International Nuclear Information System (INIS)

    Eschwege, Karel G. von; As, Lydia van; Joubert, Chris C.; Swarts, Jannie C.; Aquino, Manuel A.S.; Cameron, T. Stanley

    2013-01-01

    Graphical abstract: Electrochemically Co(HDz) 3 (5), show three main ligand-based redox processes, two reductions and one oxidation. Ligand oxidations can be resolved into three components highlighting effective intramolecular interactions between molecular fragments; a spectroelectrochemical study of (5) highlighted spectroscopic changes during the six observed redox steps. - Highlights: • Comparative CV's of dithizone (1), PhHg(HDz) and new Co(HDz) 3 (5), is discussed. • One oxidation and two reductions per ligand and a Co III/II couple for (5) are observed. • Mono- and tris-coordinated PhHg(HDz) and (5) have stable metal thioether bonds. • Crystal structure details explain good resolution between ligand redox processes. • Spectro-electrochemistry of (5) highlights spectroscopic properties of redox products. - Abstract: The reactions between dithizone (H 2 Dz (1)) or potassium dithizonate (KHDz (3)), and [Co(H 2 O) 6 ] 2+ (6), in acetone or methanol to liberate tris-dithizonatocobalt(III), Co(HDz) 3 (5), are described. The structure of (5) was confirmed by single crystal X-ray analyses and shows bidentate coordination to Co III via S and N donor atoms for all three HDz − ligands. A comparative voltammetric and spectro-electrochemical study revealed that (1) can be oxidised in two one-electron transfer steps, to generate a disulphide first and then HDz + . In contrast, upon complexation with cobalt, the free mercaptan group of (1) becomes a stable “metal thioether”, Co-S-C, which effectively prevents disulphide formation in all three ligands of (5) upon electrochemical oxidation. As a result, each ligand of Co(HDz) 3 shows just one oxidation process. Intramolecular communication between ligands is evident because the three separate ligand-based oxidations are well resolved. Two irreversible ligand reduction steps, each consisting of three unresolved components related to each of the three ligands, were also observed. The Co II /Co III couple

  12. Absence of Intramolecular Singlet Fission in Pentacene-Perylenediimide Heterodimers: The Role of Charge Transfer State.

    Science.gov (United States)

    Wang, Long; Wu, Yishi; Chen, Jianwei; Wang, Lanfen; Liu, Yanping; Yu, Zhenyi; Yao, Jiannian; Fu, Hongbing

    2017-11-16

    A new class of donor-acceptor heterodimers based on two singlet fission (SF)-active chromophores, i.e., pentacene (Pc) and perylenediimide (PDI), was developed to investigate the role of charge transfer (CT) state on the excitonic dynamics. The CT state is efficiently generated upon photoexcitation. However, the resulting CT state decays to different energy states depending on the energy levels of the CT state. It undergoes extremely rapid deactivation to the ground state in polar CH 2 Cl 2 , whereas it undergoes transformation to a Pc triplet in nonpolar toluene. The efficient triplet generation in toluene is not due to SF but CT-mediated intersystem crossing. In light of the energy landscape, it is suggested that the deep energy level of the CT state relative to that of the triplet pair state makes the CT state actually serve as a trap state that cannot undergoes an intramolecular singlet fission process. These results provide guidance for the design of SF materials and highlight the requisite for more widely applicable design principles.

  13. Enantioselective synthesis of almorexant via iridium-catalysed intramolecular allylic amidation

    NARCIS (Netherlands)

    Fananas Mastral, Martin; Teichert, Johannes F.; Fernandez-Salas, Jose Antonio; Heijnen, Dorus; Feringa, Ben L.

    2013-01-01

    An enantioselective synthesis of almorexant, a potent antagonist of human orexin receptors, is presented. The chiral tetrahydroisoquinoline core structure was prepared via iridium-catalysed asymmetric intramolecular allylic amidation. Further key catalytic steps of the synthesis include an oxidative

  14. Hydrogen bond strengthening induces fluorescence quenching of PRODAN derivative by turning on twisted intramolecular charge transfer

    Science.gov (United States)

    Yang, Yonggang; Li, Donglin; Li, Chaozheng; Liu, YuFang; Jiang, Kai

    2017-12-01

    Researchers have proposed different effective mechanisms of hydrogen bonding (HB) on the fluorescence of 6-propionyl-2-dimethylaminonaphthalene (PRODAN) and its derivatives. Herein, excited state transition and dynamics analysis confirm that the fluorescence of PD (a derivative of PRODAN with ethyl replaced by 3-hydroxy-2,2-dimethylpropan) emits from the planar intramolecular charge transfer (PICT) state rather than twist ICT (TICT) state, because the fluorescence emission and surface hopping from the TICT state to the twist ground (T-S0) state is energy forbidden. Nevertheless, the strengthening of intramolecular-HB (intra-HB) and intermolecular-HB (inter-HB) of PD-(methanol)2 smooth the pathway of surface hopping from TICT to T-S0 state and the external conversion going to planar ground state by decreasing the energy difference of the two states. This smoothing changes the fluorescence state of PD-(methanol)2 to the TICT state in which fluorescence emission does not occur but surface hopping, leading to the partial fluorescence quenching of PD in methanol solvent. This conclusion is different from previous related reports. Moreover, the inter-HB strengthening of PD-methanol in PICT state induces the cleavage of intra-HB and a fluorescence red-shift of 54 nm compared to PD. This red-shift increases to 66 nm for PD-(methanol)2 for the strengthening of the one intra-HB and two inter-HBs. The dipole moments of PD-methanol and PD-(methanol)2 respectively increase about 10.3D and 8.1D in PICT state compared to PD. The synergistic effect of intra-HB and inter-HB induces partial quenching of PD in methanol solvent by turning on the TICT state and fluorescence red-shift. This work gives a reasonable description on the fluorescence red-shift and partial quenching of PD in methanol solvent, which will bring insight into the study of spectroscopic properties of molecules owning better spectral characteristics.

  15. Intramolecular Crosstalk between Catalytic Activities of Receptor Kinases

    KAUST Repository

    Kwezi, Lusisizwe

    2018-01-22

    Signal modulation is important for the growth and development of plants and this process is mediated by a number of factors including physiological growth regulators and their associated signal transduction pathways. Protein kinases play a central role in signaling, including those involving pathogen response mechanisms. We previously demonstrated an active guanylate cyclase (GC) catalytic center in the brassinosteroid insensitive receptor (AtBRI1) within an active intracellular kinase domain resulting in dual enzymatic activity. Here we propose a novel type of receptor architecture that is characterized by a functional GC catalytic center nested in the cytosolic kinase domain enabling intramolecular crosstalk. This may be through a cGMP-AtBRI1 complex forming that may induce a negative feedback mechanism leading to desensitisation of the receptor, regulated through the cGMP production pathway. We further argue that the comparatively low but highly localized cGMP generated by the GC in response to a ligand is sufficient to modulate the kinase activity. This type of receptor therefore provides a molecular switch that directly and/or indirectly affects ligand dependent phosphorylation of downstream signaling cascades and suggests that subsequent signal transduction and modulation works in conjunction with the kinase in downstream signaling.

  16. Intramolecular Crosstalk between Catalytic Activities of Receptor Kinases

    KAUST Repository

    Kwezi, Lusisizwe; Wheeler, Janet I; Marondedze, Claudius; Gehring, Christoph A; Irving, Helen R

    2018-01-01

    Signal modulation is important for the growth and development of plants and this process is mediated by a number of factors including physiological growth regulators and their associated signal transduction pathways. Protein kinases play a central role in signaling, including those involving pathogen response mechanisms. We previously demonstrated an active guanylate cyclase (GC) catalytic center in the brassinosteroid insensitive receptor (AtBRI1) within an active intracellular kinase domain resulting in dual enzymatic activity. Here we propose a novel type of receptor architecture that is characterized by a functional GC catalytic center nested in the cytosolic kinase domain enabling intramolecular crosstalk. This may be through a cGMP-AtBRI1 complex forming that may induce a negative feedback mechanism leading to desensitisation of the receptor, regulated through the cGMP production pathway. We further argue that the comparatively low but highly localized cGMP generated by the GC in response to a ligand is sufficient to modulate the kinase activity. This type of receptor therefore provides a molecular switch that directly and/or indirectly affects ligand dependent phosphorylation of downstream signaling cascades and suggests that subsequent signal transduction and modulation works in conjunction with the kinase in downstream signaling.

  17. TDDFT study on intramolecular hydrogen bond of photoexcited methyl salicylate.

    Science.gov (United States)

    Qu, Peng; Tian, Dongxu

    2014-01-01

    The equilibrium geometries, IR-spectra and transition mechanism of intramolecular hydrogen-bonded methyl salicylate in excited state were studied using DFT and TDDFT with 6-31++G (d, p) basis set. The length of hydrogen bond OH⋯OC is decreased from 1.73 Å in the ground state to 1.41 and 1.69 Å in the excited S1 and S3 states. The increase of bond length for HO and CO group also indicates that in excited state the hydrogen bond OH⋯OC is strengthened. IR spectra show HO and CO stretching bands are strongly redshifted by 1387 and 67 cm(-1) in the excited S1 and S3 states comparing to the ground state. The excitation energy and the absorption spectrum show the S3 state is the main excited state of the low-lying excited states. By analyzing the frontier molecular orbitals, the transition from the ground state to the excited S1 and S3 states was predicted to be the π→π∗ mode. Copyright © 2013 Elsevier B.V. All rights reserved.

  18. Intramolecular oxidative deselenization of acylselenoureas: a facile synthesis of benzoxazole amides and carbonic anhydrase inhibitors.

    Science.gov (United States)

    Angeli, A; Peat, T S; Bartolucci, G; Nocentini, A; Supuran, C T; Carta, F

    2016-12-28

    A mild, efficient and one pot procedure to access benzoxazoles using easily accessible acylselenoureas as starting materials has been discovered. Mechanistic studies revealed a pH dependent intramolecular oxidative deselenization, with ring closure due to an intramolecular nucleophilic attack of a phenoxide ion. All the benzoxazoles herein reported possessed a primary sulfonamide zinc binding group and showed effective inhibitory action on the enzymes, carbonic anhydrases.

  19. 11th International Conference on Clustering Aspects of Nuclear Structure and Dynamics

    International Nuclear Information System (INIS)

    2017-01-01

    Preface The 11 th edition of the International Conference on Clustering Aspects of Nuclear Structure and Dynamics (CLUSTER‘16) was held in Napoli, Italy, on May 23-27 2016. All the Conference Sessions took place in the magnificent Complesso Monumentale dei Ss. Marcellino e Festo , located in the Historical Centre of Naples. This is one of the most prestigious building complexes of the Federico II University of Naples, the main home institution of the organizers, together with the Istituto Nazionale di Fisica Nucleare (Naples division). This building is 500 years old; in the XVIII century, it was reshaped by Luigi Vanvitelli, a famous architect of the pre-Neoclassical period in Italy, designer of the prestigious Royal Palace in the near town of Caserta. The site of Plenary Sessions was the Church of Ss. Marcellino e Festo , where all the participants were surrounded by the Baroque frescoes by Belisario Corenzio and, among the others, the paintings of Battistello Caracciolo, Massimo Stanzione, Giuseppe Simonelli and Francesco De Mura, important artists of the late Baroque period in South Italy. The sites of Parallel Sessions were two halls in the arcade of the S. Marcellino cloister: this gave the opportunity to the participants to enjoy the beauty of the architecture of the cloister with its fountains, gardens, sculptures. As organizers of the Conference, our main aims were: (1) to provide an excellent programme, with the expectation to be a reference point for the Nuclear Cluster Physics in the next four years; (2) to assure a very relaxing stay to the participants, allowing them to explore the bounty of artistic, and also culinary, masterpieces that Naples offers to its guests. The first point was assured by all the conveners that, with their excellent talks, gave a very precise and complete overview of the most recent achievements on Nuclear Cluster Physics, both from the experimental and theoretical point of view. We are indebted with the International

  20. A molecular dynamics analysis of internal friction effects on the plasticity of Zr65Cu35 metallic glass

    International Nuclear Information System (INIS)

    Feng, Shidong; Qi, Li; Zhao, Fengli; Pan, Shaopeng; Li, Gong; Ma, Mingzhen; Liu, Riping

    2015-01-01

    Highlights: • Effects of internal friction on plasticity is investigated at the atomic level. • The simulations allow reproduction of images of internal friction evolution. • The simulation results are in good agreement with experiments and theories. • This simulation can predict the deformation mode with different internal friction. - Abstract: The effects of internal friction (IF) on Zr 65 Cu 35 metallic glass plasticity are investigated through molecular dynamics simulations. Results show that the Voronoi polyhedron 〈0, 3, 6, 3〉 increases as IF increases, thereby effectively inhibiting localized deformation and improving metallic glass plasticity. The simulations allow reproduction of images of IF evolution in metallic glasses subjected to isothermal annealing at 730 K and 850 K respectively, which can help explain the experimental observations. IF could be adjusted by selecting suitable annealing temperatures and cooling rates. The results of this work provide a strong foundation for future metallic glass designs

  1. A study on the change in dynamic characteristics of reactor internals

    International Nuclear Information System (INIS)

    Kim, Tae Ryong; Jung, Seung Ho; Park, Jin Ho; Park, Jin Suk; Jeong, Keong Hoon

    1993-12-01

    An experimental and analytical studies were performed to establish the relationship between in-air dynamic characteristics of reactor internals and in-water ones by using a scaled-down model which consists of CSB (flexible) and RPV (rigid) models. The experimental results show that the natural frequencies of the CSB model in water are remarkably lowered than those in air, and the normalized natural frequency (in-water frequency/in-air frequency) of the CSB model exists between in-phase mode and out-of-phase mode values of the flexible-to-flexible co-axial cylindrical structure which has the same dimensions as the scaled-down model. The normalized frequency increases to asymptotically reach the in-phase mode frequency of the flexible co-axial cylindrical structure as circumferential mode number (n) increases, while decreases to come near of the out-of-phase mode value as the circumferential mode number decreases. The support condition change for the CSB model in waster made the frequency of 1st axial mode (pure beam mode) shifted into lower value without any effect on the other modes. The changing trend of the natural frequencies and the mode shapes resulted from the finite element analysis by using the ANSYS code shows good agreement with the experimental results both in air and in water cases. In addition, a theoretical study was also performed by simplifying the scaled-down model as flexible-to-rigid co-axial cylindrical structure. It is found that the in-air natural frequencies shows good agreement with both the experimental and finite element analysis results, while the in-water frequencies reveals rather discrepancies. (Author)

  2. The Traumatogenic Dynamics of Internalized Stigma of Mental Illness Among Arab American, Muslim, and Refugee Clients.

    Science.gov (United States)

    Kira, Ibrahim A; Lewandowski, Linda; Ashby, Jeffrey S; Templin, Thomas; Ramaswamy, Vidya; Mohanesh, Jamal

    2014-07-01

    Understanding the dynamics of mental health stigma through existing frameworks, especially in minorities with higher stigma, is problematic. There is a need to reconceptualize stigma, particularly in highly traumatized groups. The current study examines the validity of a new development-based trauma framework that conceptualizes stigma as a type III chronic trauma that contributes to negative mental health effects. This framework proposes that public stigma is a unique chronic traumatic stress that mediates the effects of similar trauma types in mental health patients. To test this proposition, this study explores the relationships between internalized stigma of mental illness (ISMI), different trauma types, and posttrauma spectrum disorders. ISMI, posttraumatic stress disorder, other posttrauma spectrum disorders, and cumulative trauma measures were administered to a sample of 399 mental health patients that included Arab (82%), Muslim (84%), and refugee (31%), as well as American patients (18%). Age in the sample ranged from 18 to 76 years (M = 39.66, SD = 11.45), with 53.5% males. Hierarchical multiple regression, t tests, and path analyses were conducted. Results indicated that ISMI predicted posttraumatic stress disorder and other posttrauma spectrum disorders after controlling for cumulative trauma. ISMI was associated with other chronic collective identity traumas. While Arab Americans, Muslims, and refugees had higher ISMI scores than other Americans, the elevated chronic trauma levels of these groups were significant predictors of these differences. The results provide evidence to support ISMI traumatology model. Implications of the results for treating victims of ISMI, especially Arab Americans, Muslims and refugees are discussed. © The Author(s) 2014.

  3. Proceedings of the International Symposium on Dynamics of Fluids in Fractured Rocks: Concepts and Recent Advances

    Energy Technology Data Exchange (ETDEWEB)

    Faybishenko, B. (ed.)

    1999-02-01

    This publication contains extended abstracts of papers presented at the International Symposium ''Dynamics of Fluids in Fractured Rocks: Concepts and Recent Advances'' held at Ernest Orlando Lawrence Berkeley National Laboratory on February 10-12, 1999. This Symposium is organized in Honor of the 80th Birthday of Paul A. Witherspoon, who initiated some of the early investigations on flow and transport in fractured rocks at the University of California, Berkeley, and at Lawrence Berkeley National Laboratory. He is a key figure in the development of basic concepts, modeling, and field measurements of fluid flow and contaminant transport in fractured rock systems. The technical problems of assessing fluid flow, radionuclide transport, site characterization, modeling, and performance assessment in fractured rocks remain the most challenging aspects of subsurface flow and transport investigations. An understanding of these important aspects of hydrogeology is needed to assess disposal of nu clear wastes, development of geothermal resources, production of oil and gas resources, and remediation of contaminated sites. These Proceedings of more than 100 papers from 12 countries discuss recent scientific and practical developments and the status of our understanding of fluid flow and radionuclide transport in fractured rocks. The main topics of the papers are: Theoretical studies of fluid flow in fractured rocks; Multi-phase flow and reactive chemical transport in fractured rocks; Fracture/matrix interactions; Hydrogeological and transport testing; Fracture flow models; Vadose zone studies; Isotopic studies of flow in fractured systems; Fractures in geothermal systems; Remediation and colloid transport in fractured systems; and Nuclear waste disposal in fractured rocks.

  4. Internal cycling, not external loading, decides the nutrient limitation in eutrophic lake: A dynamic model with temporal Bayesian hierarchical inference.

    Science.gov (United States)

    Wu, Zhen; Liu, Yong; Liang, Zhongyao; Wu, Sifeng; Guo, Huaicheng

    2017-06-01

    Lake eutrophication is associated with excessive anthropogenic nutrients (mainly nitrogen (N) and phosphorus (P)) and unobserved internal nutrient cycling. Despite the advances in understanding the role of external loadings, the contribution of internal nutrient cycling is still an open question. A dynamic mass-balance model was developed to simulate and measure the contributions of internal cycling and external loading. It was based on the temporal Bayesian Hierarchical Framework (BHM), where we explored the seasonal patterns in the dynamics of nutrient cycling processes and the limitation of N and P on phytoplankton growth in hyper-eutrophic Lake Dianchi, China. The dynamic patterns of the five state variables (Chla, TP, ammonia, nitrate and organic N) were simulated based on the model. Five parameters (algae growth rate, sediment exchange rate of N and P, nitrification rate and denitrification rate) were estimated based on BHM. The model provided a good fit to observations. Our model results highlighted the role of internal cycling of N and P in Lake Dianchi. The internal cycling processes contributed more than external loading to the N and P changes in the water column. Further insights into the nutrient limitation analysis indicated that the sediment exchange of P determined the P limitation. Allowing for the contribution of denitrification to N removal, N was the more limiting nutrient in most of the time, however, P was the more important nutrient for eutrophication management. For Lake Dianchi, it would not be possible to recover solely by reducing the external watershed nutrient load; the mechanisms of internal cycling should also be considered as an approach to inhibit the release of sediments and to enhance denitrification. Copyright © 2017 Elsevier Ltd. All rights reserved.

  5. Dynamic analysis of electron density in the course of the internal motion of molecular system

    International Nuclear Information System (INIS)

    Tachibana, A.; Hori, K.; Asai, Y.; Yamabe, T.

    1984-01-01

    The general dynamic aspect of electron density of a molecular system is studied on the basis of the general equation of the electron orbital which is formulated for the dynamic study of electronic motion. The newly defined electron orbital incorporates the dynamics of molecular vibration into the electronic structures. In this scheme, the change of electron distribution caused by excitation of vibrational state is defined as the ''dynamic electron transfer.'' The dynamic electron density is found to have the remarkable ''additive'' property. The time-dependent aspect of the dynamic electron redistribution is also analyzed on the basis of the ''coherent state.'' The new method relates the classical vibrational amplitude to the quantum number of the vibrational state. As a preliminary application of the present treatment, the dynamic electron densities of H 2 , HD, HT, HF, and HCl molecules are calculated by use of ab initio molecular orbital method

  6. Internal Migration of Canadian Immigrants, 1993-2004: Evidence from the Survey of Labour and Income Dynamics

    Directory of Open Access Journals (Sweden)

    K. Bruce Newbold

    2011-01-01

    Full Text Available Combining the 1993, 1996, and 1999 six-year panels of the Survey of Labour and Income Dynamics Master Files, the purpose of the paper is twofold. First, it examines the migration and distribution patterns of the foreign-born across Census Metropolitan Areas (CMAs. Second, it examines how internal migration modeling results may differ whether pre- and post-migration measures are used. Results suggest that internal migration of the foreign-born generally does not increase their dispersion across Canada, with the foreign-born primarily choosing one of the three immigrant gateway cities of Toronto, Montreal and Vancouver, or moving to other relatively large CMAs.

  7. The impact of seasonal changes in stratification on the dynamics of internal waves in the Sea of Okhotsk

    Directory of Open Access Journals (Sweden)

    Oxana E. Kurkina

    2017-11-01

    Full Text Available The properties and dynamics of internal waves in the ocean crucially depend on the vertical structure of water masses. We present detailed analysis of the impact of spatial and seasonal variations in the density-driven stratification in the Sea of Okhotsk on the properties of the classic kinematic and nonlinear parameters of internal waves in this water body. The resulting maps of the phase speed of long internal waves and coefficients at various terms of the underlying Gardner’s equation make it possible to rapidly determine the main properties of internal solitary waves in the region and to choose an adequate set of parameters of the relevant numerical models. It is shown that the phase speed of long internal waves almost does not depend on the particular season. The coefficient at the quadratic term of the underlying evolution equation is predominantly negative in summer and winter and therefore internal solitons usually have negative polarity. Numerical simulations of the formation of internal solitons and solibores indicate that seasonal variations in the coefficient at the cubic term of Gardner’s equation lead to substantial variations in the shape of solibores.

  8. Intramolecular excimer formation of diastereoisomeric model compounds of polystyrene in fluid solution: their local molecular motion and photophysical properties

    International Nuclear Information System (INIS)

    Itagaki, Hideyuki; Horie, Kazuyuki; Mita, Itaru; Washio, Masakazu; Tagawa, Seiichi; Tabata, Yoneho

    1989-01-01

    The dynamic process of intramolecular excimer formation in diasteroisomeric oligomers model compounds of polystyrene, was investigated by using a picosecond pulse radiolysis technique. Monomer fluorescence of all-racemic isomers decays single-exponentially, while that of other isomers decays dual-exponentially. Multicomponent fluorescence decay curves are supposed to be mainly induced by conformational changes. The results suggest that the excimer in oligostyrenes (or polystyrene) is formed mainly in meso diad. It is definitely proved that there exists singlet energy migration in styrene trimer and tetramer systems. The conformational change in PS3 and PS4 is concluded to occur by way of cooperative motions in backbone chains bond such as a crankshaft transition, not by way of independent rotation around each carbon-carbon bond of the backbone chain. (author)

  9. [Differences in dynamics of insulin and insulin-like growth I (IGF-I) receptors internalization in isolated rat hepatocytes].

    Science.gov (United States)

    Kolychev, A P; Ternovskaya, E E; Arsenieva, A V; Shapkina, E V

    2013-01-01

    Insulin and IGF-I are two related peptides performing in the mammalian body functionally different roles of the metabolic and growth hormones, respectively. Internalization of the insulin-receptor complex (IRC) is the most important chain of mechanism of the action of hormone. To elucidate differences in the main stages of internalization of the two related hormones, the internalization dynamics of 125I-insulin and 125I-IGF-I was traced in isolated rat hepatocytes at 37 and 12 degrees C. There were established marked differences in the process of internalization of labeled hormones, which is stimulated by insulin and IGF-I. At 37 degrees C the insulin-stimulated internalization, unlike the process initiated by IGF-I, did not reach the maximal level for 1 h of incubation. However, essential differences in the internalization course of these two related peptide were obvious at the temperature of 12 degrees C. The internalization level of insulin receptors at 12 degrees C decreased by one third in spite of a significant increase of the insulin receptor binding on the hepatocytes plasma membrane. At 12 degrees C a slight decrease of the proportion of intracellular 125I-IGF-I correlated with a decrease in the 125I-IGF-I binding to receptors on the cell membrane. Internalization of IGF-I receptors was not affected by low temperature, as neither its level, nor the rate changed at 12 degrees C. The paradoxical decrease of the insulin-stimulated internalization at low temperature seems to represent a peculiar "inhibition mechanism" of immersion of IRC into the cell, which leads to accumulation of the complexes on the cell surface and possibly to a readjustment of the insulin biological activity. The resistance of internalization of the IGF-I receptor to cold seems to be related to the more ancient origin of this mechanism in the poikilothermal vertebrates.

  10. New fast organic scintillators using intramolecular bromine quenching

    International Nuclear Information System (INIS)

    Berlman, I.B.; Lutz, S.S.; Flournoy, J.M.; Ashford, C.B.; Franks, L.A.

    1984-01-01

    Organic scintillator solutions with decay times as fast as 500 ps and with relatively high conversion efficiencies have been developed. The intramolecular quenching was achieved through the novel approach of adding a bromine atom to the 3- or 4-position of para-oligophenylenes, the fluorescent solutes in these binary solutions. The bromine serves to enhance singlet-to-triplet intersystem crossing in the chromophore, causing a reduction in the scintillation yield and a concomitant reduction in the decay time. The very fast value given above probably also involves some intermolecular self-quenching at high concentration. In addition, the bromine reduces the symmetry of the molecules, thereby increasing their solubility. Finally, an alkyl chain on the opposite para position further increases the solubility and also increases the immunity of the chromophore to quenching. The decay times for binary liquid solutions in toluene (at the indicated concentrations) were 0.51 ns for 4-BHTP (0.14 M), 0.75 ns for 3-BHTP (0.14 M), 0.57 ns for 3-BTP (0.14 M), and 1.3 ns for 4-BHQP (0.06 M). Binary plastics with 4-BHTP as the solute in concentrations up to 0.14 M were cast in polystyrene. The shortest decay time, 0.40 ns, was measured for the 0.14 M concentration. A plastic scintillator containing 3-BTP (0.11 M in polystyrene) had a decay time of 0.85 ns. These results compare favorably with the plastic scintillator BC-422 whose decay time is about 1.4 ns. (orig./HSI)

  11. FOREWORD: International Summer School for Advanced Studies 'Dynamics of open nuclear systems' (PREDEAL12)

    Science.gov (United States)

    Delion, D. S.; Zamfir, N. V.; Raduta, A. R.; Gulminelli, F.

    2013-02-01

    This proceedings volume contains the invited lectures and contributions presented at the International Summer School on Nuclear Physics held at Trei Brazi, a summer resort of the Bioterra University, near the city of Predeal, Romania, on 9-20 July 2012. The long tradition of International Summer Schools on Nuclear Physics in Romania dates as far back as 1964, with the event being scheduled every two years. During this period of almost 50 years, many outstanding nuclear scientists have lectured on various topics related to nuclear physics and particle physics. This year we celebrate the 80th birthday of Aureliu Sandulescu, one of the founders of the Romanian school of theoretical nuclear physics. He was Serban Titeica's PhD student, one of Werner Heisenberg's PhD students, and he organized the first edition of this event. Aureliu Sandulescu's major contributions to the field of theoretical nuclear physics are related in particular to the prediction of cluster radioactivity, the physics of open quantum systems and the innovative technique of detecting superheavy nuclei using the double magic projectile 48Ca (Calcium), nowadays a widely used method at the JINR—Dubna and GSI—Darmstadt laboratories. The title of the event, 'Dynamics of Open Nuclear Systems', is in recognition of Aureliu Sandulescu's great personality. The lectures were attended by Romanian and foreign Master and PhD students and young researchers in nuclear physics. About 25 reputable professors and researchers in nuclear physics delivered lectures during this period. According to a well-established tradition, an interval of two hours was allotted for each lecture (including discussions). Therefore we kept a balance between the school and conference format. Two lectures were held during the morning and afternoon sessions. After lecture sessions, three or four oral contributions were given by young scientists. This was a good opportunity for them to present the results of their research in front of

  12. A review of a method for dynamic load distribution, dynamical modeling, and explicit internal force control when two manipulators mutually lift and transport a rigid body object

    International Nuclear Information System (INIS)

    Unseren, M.A.

    1997-01-01

    The paper reviews a method for modeling and controlling two serial link manipulators which mutually lift and transport a rigid body object in a three dimensional workspace. A new vector variable is introduced which parameterizes the internal contact force controlled degrees of freedom. A technique for dynamically distributing the payload between the manipulators is suggested which yields a family of solutions for the contact forces and torques the manipulators impart to the object. A set of rigid body kinematic constraints which restrict the values of the joint velocities of both manipulators is derived. A rigid body dynamical model for the closed chain system is first developed in the joint space. The model is obtained by generalizing the previous methods for deriving the model. The joint velocity and acceleration variables in the model are expressed in terms of independent pseudovariables. The pseudospace model is transformed to obtain reduced order equations of motion and a separate set of equations governing the internal components of the contact forces and torques. A theoretic control architecture is suggested which explicitly decouples the two sets of equations comprising the model. The controller enables the designer to develop independent, non-interacting control laws for the position control and internal force control of the system

  13. A review of a method for dynamic load distribution, dynamical modeling, and explicit internal force control when two manipulators mutually lift and transport a rigid body object

    Energy Technology Data Exchange (ETDEWEB)

    Unseren, M.A.

    1997-04-20

    The paper reviews a method for modeling and controlling two serial link manipulators which mutually lift and transport a rigid body object in a three dimensional workspace. A new vector variable is introduced which parameterizes the internal contact force controlled degrees of freedom. A technique for dynamically distributing the payload between the manipulators is suggested which yields a family of solutions for the contact forces and torques the manipulators impart to the object. A set of rigid body kinematic constraints which restrict the values of the joint velocities of both manipulators is derived. A rigid body dynamical model for the closed chain system is first developed in the joint space. The model is obtained by generalizing the previous methods for deriving the model. The joint velocity and acceleration variables in the model are expressed in terms of independent pseudovariables. The pseudospace model is transformed to obtain reduced order equations of motion and a separate set of equations governing the internal components of the contact forces and torques. A theoretic control architecture is suggested which explicitly decouples the two sets of equations comprising the model. The controller enables the designer to develop independent, non-interacting control laws for the position control and internal force control of the system.

  14. A dynamic model and an experimental study for the internal air and soil temperatures in an innovative greenhouse

    International Nuclear Information System (INIS)

    Joudi, Khalid A.; Farhan, Ammar A.

    2015-01-01

    Highlights: • Simulation model for internal Greenhouse temperature including soil reflectance. • Greenhouse soil heat exchange affects internal temperature by approximately 12%. • Solar air heaters as greenhouse roof maintain better internal temperature year round. - Abstract: An innovative greenhouse which integrates a conventional greenhouse with roof mounted solar air heaters is used in this investigation. This design reduces the solar radiation incoming to the greenhouse in summer which reduced the load and cost of greenhouse cooling and provides a means of solar heating. Experimental measurements of the internal air and internal soil sub-layer temperatures in the greenhouse, without crops, were performed in Baghdad University, Baghdad, Iraq (33.3 °N, 44.4 °E). Measurements were recorded for clear and partly cloudy winter days. A dynamic model was developed to predict the all internal temperatures of the greenhouse. This model includes soil surface heat exchange with the greenhouse air which was found to give a more accurate prediction of the internal temperatures. Soil surface heat exchange has a positive contribution to the internal environment. The input parameters of the model were the measured meteorological conditions and the thermo-physical properties of the greenhouse components which include the cover, inside air, and soil. Comparisons between the predicted and measured results show good agreement. Also, results show that soil sub-layers inside the greenhouse at 50 cm depth are the best place for heat storage elements. The integrated system rendered maximum differences between ambient and internal air temperatures of 16 °C in February and 10 °C in June without operating any heating or cooling system

  15. The internal processes and behavioral dynamics of hospital boards: an exploration of differences between high- and low-performing hospitals.

    Science.gov (United States)

    Kane, Nancy M; Clark, Jonathan R; Rivenson, Howard L

    2009-01-01

    Nonprofit hospital boards are under increasing pressure to improve financial, clinical, and charitable and community benefit performance. Most research on board effectiveness focuses on variables measuring board structure and attributes associated with competing ideal models of board roles. However, the results do not provide clear evidence that one role is superior to another and suggest that in practice boards pursue hybrid roles. Board dynamics and processes have received less attention from researchers, but emerging theoretical frameworks highlight them as key to effective corporate governance. We explored differences in board processes and behavioral dynamics between financially high- and low-performing hospitals, with the goal of developing a better understanding of the best board practices in nonprofit hospitals. A comparative case study approach allowed for in-depth, qualitative assessments of how the internal workings of boards differ between low- and high-performing facilities. Boards of hospitals with strong financial performance exhibited behavioral dynamics and internal processes that differed in important ways from those of hospitals with poor financial performance. Boards need to actively attend to key processes and foster positive group dynamics in decision making to be more effective in governing hospitals.

  16. Effect of bidirectional internal flow on fluid–structure interaction dynamics of conveying marine riser model subject to shear current

    Directory of Open Access Journals (Sweden)

    Zheng-Shou Chen

    2012-03-01

    Full Text Available This article presents a numerical investigation concerning the effect of two kinds of axially progressing internal flows (namely, upward and downward on fluid–structure interaction (FSI dynamics about a marine riser model which is subject to external shear current. The CAE technology behind the current research is a proposed FSI solution, which combines structural analysis software with CFD technology together. Efficiency validation for the CFD software was carried out first. It has been proved that the result from numerical simulations agrees well with the observation from relating model test cases in which the fluidity of internal flow is ignorable. After verifying the numerical code accuracy, simulations are conducted to study the vibration response that attributes to the internal progressive flow. It is found that the existence of internal flow does play an important role in determining the vibration mode (/dominant frequency and the magnitude of instantaneous vibration amplitude. Since asymmetric curvature along the riser span emerges in the case of external shear current, the centrifugal and Coriolis accelerations owing to up- and downward internal progressive flows play different roles in determining the fluid–structure interaction response. The discrepancy between them becomes distinct, when the velocity ratio of internal flow against external shear current is relatively high.

  17. Internal Innovation and Informational Dynamics within Small and Medium Beef Cattle Farm Enterprises

    OpenAIRE

    Noble, Chris

    2011-01-01

    The internal knowledge capabilities of small and medium beef cattle farm enterprises are examined using information economics to gain an understanding of how these organisations approach innovation. Enterprises are viewed as being embedded in the wider industry and are subject to both external and internal influences. However the discussion here is focused on internal activities in order to consider how enterprise specific knowledge is constructed allowing innovation to occur. Innovation is a...

  18. Global monitoring of dynamic information systems a case study in the international supply chain

    NARCIS (Netherlands)

    Pruksasri, P.; Berg, J. van den; Hofman, W.J.

    2014-01-01

    Global information systems are becoming more complex and dynamic everyday: huge amounts of data and messages through those systems show dynamically changing traffic patterns. Because of this, diagnosing when sub-systems are not working properly is difficult. System failures or errors in information

  19. Around the Fishing Net: Leadership Dynamics for Change in an American International School

    Science.gov (United States)

    Murakami-Ramalho, Elizabeth; Benham, Maenette

    2010-01-01

    This study explored the active involvement of school and community members investing in leadership dynamics for change, especially considering the increasingly globalized world and the importance of preparing globally minded citizens. To explore how educators and leaders work to foster dynamic learning experiences in a highly mobile global…

  20. 13th International Conference on Motion and Vibration Control (MOVIC 2016) and the 12th International Conference on Recent Advances in Structural Dynamics (RASD 2016)

    International Nuclear Information System (INIS)

    2016-01-01

    This volume contains the papers presented at the Thirteenth International Conference on Motion and Vibration Control (MoViC), together with the Twelfth International Conference on Recent Advances in Structural Dynamics (RASD). MoViC is an event that started in Yokohama, Japan in 1992 and has been organised every two years alternating between Japan, USA and Europe. The eleven previous RASD conferences have been held every three years or so since 1980 primarily in Southampton, UK. The idea of joining the two conferences came quite naturally because of the common ground of the two conferences and the chances of cross-pollination between two otherwise separate research groups. This joint conference is devoted to theoretical, numerical and experimental developments in motion/vibration/structural dynamics, their control and application to all types of structures and dynamical systems. The conference reflects the state-of-the- art in these topics, and is an excellent opportunity to exchange scientific, technical and experimental ideas. The Conference Proceedings include over 250 papers by authors from over 20 countries, forty technical sessions and five plenary presentations. The five invited speakers are Professor Roger Goodall (Loughborough University, UK) presenting “Motion and vibration control for railway vehicles”, Professor Takeshi Mizuno (Saitama University, Japan) presenting “Recent advances in magnetic suspension technology”, Professor Kevin Murphy (University of Louisville, USA) presenting “Dynamics of Passive Balancing Rings for Rotating Systems”, Professor David Wagg (University of Sheffield, UK) presenting “Reducing vibrations in structures using structural control”, and Professor Kon-Well Wang (University of Michigan, USA) presenting “From Muscles to Plants - Nature-Inspired Adaptive Metastructures for Structural Dynamics Enhancement”. I would like to thank members of the Organising Committee for their help, over the last year or so, in

  1. International trade in services developments in light of dynamic developments in competitive environment

    Directory of Open Access Journals (Sweden)

    Anna Olefir

    2008-06-01

    Full Text Available The paper analyses theoretical grounds for determining «services», key peculiarities of international trade in services and its discrepancies from trade in goods, and determines the modern trends of development of this form of international trade according to the main types of services.

  2. International

    International Nuclear Information System (INIS)

    Anon.

    1997-01-01

    This rubric reports on 10 short notes about international economical facts about nuclear power: Electricite de France (EdF) and its assistance and management contracts with Eastern Europe countries (Poland, Hungary, Bulgaria); Transnuclear Inc. company (a 100% Cogema daughter company) acquired the US Vectra Technologies company; the construction of the Khumo nuclear power plant in Northern Korea plays in favour of the reconciliation between Northern and Southern Korea; the delivery of two VVER 1000 Russian reactors to China; the enforcement of the cooperation agreement between Euratom and Argentina; Japan requested for the financing of a Russian fast breeder reactor; Russia has planned to sell a floating barge-type nuclear power plant to Indonesia; the control of the Swedish reactor vessels of Sydkraft AB company committed to Tractebel (Belgium); the renewal of the nuclear cooperation agreement between Swiss and USA; the call for bids from the Turkish TEAS electric power company for the building of the Akkuyu nuclear power plant answered by three candidates: Atomic Energy of Canada Limited (AECL), Westinghouse (US) and the French-German NPI company. (J.S.)

  3. Conductance and activation energy for electron transport in series and parallel intramolecular circuits.

    Science.gov (United States)

    Hsu, Liang-Yan; Wu, Ning; Rabitz, Herschel

    2016-11-30

    We investigate electron transport through series and parallel intramolecular circuits in the framework of the multi-level Redfield theory. Based on the assumption of weak monomer-bath couplings, the simulations depict the length and temperature dependence in six types of intramolecular circuits. In the tunneling regime, we find that the intramolecular circuit rule is only valid in the weak monomer coupling limit. In the thermally activated hopping regime, for circuits based on two different molecular units M a and M b with distinct activation energies E act,a > E act,b , the activation energies of M a and M b in series are nearly the same as E act,a while those in parallel are nearly the same as E act,b . This study gives a comprehensive description of electron transport through intramolecular circuits from tunneling to thermally activated hopping. We hope that this work can motivate additional studies to design intramolecular circuits based on different types of building blocks, and to explore the corresponding circuit laws and the length and temperature dependence of conductance.

  4. Modeling the lubrication, dynamics, and effects of piston dynamic tilt of twin-land oil control rings in internal combustion engines

    Energy Technology Data Exchange (ETDEWEB)

    Tian, T.; Wong, V.W.

    2000-01-01

    A theoretical model was developed to study the lubrication, friction, dynamics, and oil transport of twin-land oil control rings (TLOCR) in internal combustion engines. A mixed lubrication model with consideration of shear-thinning effects of multigrade oils was used to describe the lubrication between the running surfaces of the two lands and the liner. Oil squeezing and asperity contact were both considered for the interaction between the flanks of the TLOCR and the ring groove. Then, the moments and axial forces from TLOCR/liner lubrication and TLOCR/groove interaction were coupled into the dynamic equations of the TLOCR. Furthermore, effects of piston dynamic tilt were considered in a quasi three-dimensional manner so that the behaviors of the TLOCR at different circumferential location could be studied. As a first step, variation of the third land pressure was neglected. The model predictions were illustrated via an SI engine. One important finding is that around thrust and anti-thrust sides, the difference between the minimum oil film thickness of two lands can be as high as several micrometers due to piston dynamic tilt. As a result, at thrust and anti-thrust sides, significant oil can pass under one land of the TLOCR along the bore, although the other land perfectly seals the bore. Then, the capabilities of the model were further explained by studying the effects of ring tension and torsional resistance on the lubrication and oil transport between the lands and the liner. The effects of oil film thickness on the flanks of the ring groove on the dynamics of the TLOCR were also studied. Friction results show that boundary lubrication contributes significantly to the total friction of the TLOCR.

  5. A "continuity-index" for assessing ice-sheet dynamics from radar-sounded internal layers

    DEFF Research Database (Denmark)

    Karlsson, Nanna Bjørnholt; Rippin, David; Bingham, Robert G.

    2012-01-01

    Radio-echo sounding (RES) of polar icesheets reveals extensive internal layering. The degree of continuity of internal layering holds critical information about the ice-flow field, but previous analyses of this parameter have been limited to qualitative classifications. Here we present a new...... further support that the main trunk and tributaries are unlikely to have undergone substantial migration since the deposition of the internal layering. Significantly, our new method for analyzing internallayers is readily transferable across RES datasets, offering promise for data-led assessments of past...

  6. Dynamical and quasi-static multi-physical models of a diesel internal combustion engine using Energetic Macroscopic Representation

    International Nuclear Information System (INIS)

    Horrein, L.; Bouscayrol, A.; Cheng, Y.; El Fassi, M.

    2015-01-01

    Highlights: • Internal Combustion Engine (ICE) dynamical and static models. • Organization of ICE model using Energetic Macroscopic Representation. • Description of the distribution of the chemical, thermal and mechanical power. • Implementation of the ICE model in a global vehicle model. - Abstract: In the simulation of new vehicles, the Internal Combustion Engine (ICE) is generally modeled by a static map. This model yields the mechanical power and the fuel consumption. But some studies require the heat energy from the ICE to be considered (i.e. waste heat recovery, thermal regulation of the cabin). A dynamical multi-physical model of a diesel engine is developed to consider its heat energy. This model is organized using Energetic Macroscopic Representation (EMR) in order to be interconnected to other various models of vehicle subsystems. An experimental validation is provided. Moreover a multi-physical quasi-static model is also derived. According to different modeling aims, a comparison of the dynamical and the quasi-static model is discussed in the case of the simulation of a thermal vehicle. These multi-physical models with different simulation time consumption provide good basis for studying the effects of the thermal energy on the vehicle behaviors, including the possibilities of waste heat recovery

  7. Change of conformation and internal dynamics of supercoiled DNA upon binding of Escherichia coli single-strand binding protein

    International Nuclear Information System (INIS)

    Langowski, J.; Benight, A.S.; Fujimoto, B.S.; Schurr, J.M.; Schomburg, U.

    1985-01-01

    The influence of Escherichia coli single-strand binding (SSB) protein on the conformation and internal dynamics of pBR322 and pUC8 supercoiled DNAs has been investigated by using dynamic light scattering at 632.8 and 351.1 nm and time-resolved fluorescence polarization anisotropy of intercalated ethidium. SSB protein binds to both DNAs up to a stoichiometry that is sufficient to almost completely relax the superhelical turns. Upon saturation binding, the translational diffusion coefficients (D 0 ) of both DNAs decrease by approximately 20%. Apparent diffusion coefficients (D/sub app/) obtained from dynamic light scattering display the well-known increase with K 2 (K = scattering vector), leveling off toward a plateau value (D/sub plat/) at high K 2 . For both DNAs, the difference D/sub plat/ - D 0 increases upon relaxation of supercoils by SSB protein, which indicates a corresponding enhancement of the subunit mobilities in internal motions. Fluorescence polarization anisotropy measurements on free and complexed pBR322 DNA indicate a (predominantly) uniform torsional rigidity for the saturated DNA/SSB protein complex that is significantly reduced compared to the free DNA. These observations are all consistent with the notion that binding of SSB protein is accompanied by a gradual loss of supercoils and saturates when the superhelical twist is largely removed

  8. Sky-blue emitting bridged diiridium complexes: beneficial effects of intramolecular π-π stacking.

    Science.gov (United States)

    Congrave, Daniel G; Hsu, Yu-Ting; Batsanov, Andrei S; Beeby, Andrew; Bryce, Martin R

    2018-02-06

    The potential of intramolecular π-π interactions to influence the photophysical properties of diiridium complexes is an unexplored topic, and provides the motivation for the present study. A series of diarylhydrazide-bridged diiridium complexes functionalised with phenylpyridine (ppy)-based cyclometalating ligands is reported. It is shown by NMR studies in solution and single crystal X-ray analysis that intramolecular π-π interactions between the bridging and cyclometalating ligands rigidify the complexes leading to high luminescence quantum efficiencies in solution and in doped films. Fluorine substituents on the phenyl rings of the bridge promote the intramolecular π-π interactions. Notably, these non-covalent interactions are harnessed in the rational design and synthesis of the first examples of highly emissive sky-blue diiridium complexes featuring conjugated bridging ligands, for which they play a vital role in the structural and photophysical properties. Experimental results are supported by computational studies.

  9. Chemical origin of blue- and redshifted hydrogen bonds: intramolecular hyperconjugation and its coupling with intermolecular hyperconjugation.

    Science.gov (United States)

    Li, An Yong

    2007-04-21

    Upon formation of a H bond Y...H-XZ, intramolecular hyperconjugation n(Z)-->sigma*(X-H) of the proton donor plays a key role in red- and blueshift characters of H bonds and must be introduced in the concepts of hyperconjugation and rehybridization. Intermolecular hyperconjugation transfers electron density from Y to sigma*(X-H) and causes elongation and stretch frequency redshift of the X-H bond; intramolecular hyperconjugation couples with intermolecular hyperconjugation and can adjust electron density in sigma*(X-H); rehybridization causes contraction and stretch frequency blueshift of the X-H bond on complexation. The three factors--intra- and intermolecular hyperconjugations and rehybridization--determine commonly red- or blueshift of the formed H bond. A proton donor that has strong intramolecular hyperconjugation often forms blueshifted H bonds.

  10. Vinylcyclopropylacyl and polyeneacyl radicals. Intramolecular ketene alkyl radical additions in ring synthesis.

    Science.gov (United States)

    De Boeck, Benoit; Herbert, Nicola M A; Harrington-Frost, Nicole M; Pattenden, Gerald

    2005-01-21

    Treatment of a variety of substituted vinylcyclopropyl selenyl esters, e.g. 11, with Bu(3)SnH-AIBN in refluxing benzene leads to the corresponding acyl radical intermediates, which undergo rearrangement and intramolecular cyclisations via their ketene alkyl radical equivalents producing cyclohexenones in 50-60% yield. By contrast, treatment of conjugated triene selenyl esters, e.g. 32, with Bu(3)SnH-AIBN produces substituted 2-cyclopentenones via intramolecular cyclisations of their ketene alkyl radical intermediates. Under the same radical-initiating conditions the selenyl esters derived from o-vinylbenzoic acid and o-vinylcinnamic acid undergo intramolecular cyclisations producing 1-indanone and 5,6-dihydrobenzocyclohepten-7-one respectively in 60-70% yields. A tandem radical cyclisation from the alpha,beta,gamma,delta-diene selenyl ester 31 provides an expeditious synthesis of the diquinane 35 in 69% yield.

  11. Weak intramolecular interaction effects on the torsional spectra of ethylene glycol, an astrophysical species

    Energy Technology Data Exchange (ETDEWEB)

    Boussessi, R., E-mail: rahma.boussesi@iem.cfmac.csic.es [Departamento de Química y Física Teóricas, I. Estructura de la Materia, IEM-CSIC, Serrano 121, Madrid 28006 (Spain); Laboratoire de Spectroscopie Atomique, Moléculaire et Applications-LSAMA LR01ES09, Faculté des sciences de Tunis, Université de Tunis El Manar, 2092 Tunis (Tunisia); Senent, M. L., E-mail: ml.senent@csic.es [Departamento de Química y Física Teóricas, I. Estructura de la Materia, IEM-CSIC, Serrano 121, Madrid 28006 (Spain); Jaïdane, N. [Laboratoire de Spectroscopie Atomique, Moléculaire et Applications-LSAMA LR01ES09, Faculté des sciences de Tunis, Université de Tunis El Manar, 2092 Tunis (Tunisia)

    2016-04-28

    An elaborate variational procedure of reduced dimensionality based on explicitly correlated coupled clusters calculations is applied to understand the far infrared spectrum of ethylene-glycol, an astrophysical species. This molecule can be classified in the double molecular symmetry group G{sub 8} and displays nine stable conformers, gauche and trans. In the gauche region, the effect of the potential energy surface anisotropy due to the formation of intramolecular hydrogen bonds is relevant. For the primary conformer, stabilized by a hydrogen bond, the ground vibrational state rotational constants are computed to be A{sub 0} = 15 369.57 MHz, B{sub 0} = 5579.87 MHz, and C{sub 0} = 4610.02 MHz corresponding to differences of 6.3 MHz, 7.2 MHz, and 3.5 MHz from the experimental parameters. Ethylene glycol displays very low torsional energy levels whose classification is not straightforward and requires a detailed analysis of the torsional wavefunctions. Tunneling splittings are significant and unpredictable due to the anisotropy of the potential energy surface PES. The ground vibrational state splits into 16 sublevels separated ∼142 cm{sup −1}. The splitting of the “G1 sublevels” was calculated to be ∼0.26 cm{sup −1} in very good agreement with the experimental data (0.2 cm{sup −1} = 6.95 MHz). Transitions corresponding to the three internal rotation modes allow assignment of previously observed Q branches. Band patterns, calculated between 362.3 cm{sup −1} and 375.2 cm{sup −1}, 504 cm{sup −1} and 517 cm{sup −1}, and 223.3 cm{sup −1} and 224.1 cm{sup −1}, that correspond to the tunnelling components of the v{sub 21} fundamental (v{sub 21} = OH-torsional mode), are assigned to the prominent experimental Q branches.

  12. Excited-state intramolecular hydrogen transfer (ESIHT) of 1,8-Dihydroxy-9,10-anthraquinone (DHAQ) characterized by ultrafast electronic and vibrational spectroscopy and computational modeling

    KAUST Repository

    Mohammed, Omar F.

    2014-05-01

    We combine ultrafast electronic and vibrational spectroscopy and computational modeling to investigate the photoinduced excited-state intramolecular hydrogen-transfer dynamics in 1,8-dihydroxy-9,10-anthraquinone (DHAQ) in tetrachloroethene, acetonitrile, dimethyl sulfoxide, and methanol. We analyze the electronic excited states of DHAQ with various possible hydrogen-bonding schemes and provide a general description of the electronic excited-state dynamics based on a systematic analysis of femtosecond UV/vis and UV/IR pump-probe spectroscopic data. Upon photoabsorption at 400 nm, the S 2 electronic excited state is initially populated, followed by a rapid equilibration within 150 fs through population transfer to the S 1 state where DHAQ exhibits ESIHT dynamics. In this equilibration process, the excited-state population is distributed between the 9,10-quinone (S2) and 1,10-quinone (S1) states while undergoing vibrational energy redistribution, vibrational cooling, and solvation dynamics on the 0.1-50 ps time scale. Transient UV/vis pump-probe data in methanol also suggest additional relaxation dynamics on the subnanosecond time scale, which we tentatively ascribe to hydrogen bond dynamics of DHAQ with the protic solvent, affecting the equilibrium population dynamics within the S2 and S1 electronic excited states. Ultimately, the two excited singlet states decay with a solvent-dependent time constant ranging from 139 to 210 ps. The concomitant electronic ground-state recovery is, however, only partial because a large fraction of the population relaxes to the first triplet state. From the similarity of the time scales involved, we conjecture that the solvent plays a crucial role in breaking the intramolecular hydrogen bond of DHAQ during the S2/S1 relaxation to either the ground or triplet state. © 2014 American Chemical Society.

  13. Development of international labor migration in the dynamics of globalization processes

    Directory of Open Access Journals (Sweden)

    Rubinskaya Eteri, D.

    2015-03-01

    Full Text Available The current characteristics of international migration caused by the qualitative changes that occur in the global economy under influence of increasing globalization. The paper attempts to suggest periodization of the global economy development and to identify features of international labor migration occurred under the influence of deep changes in the world economy. During this period, the author identifies three stages in the formation of globalization, the transition criterion from one to other is the degree of world economy changes under the influence of the productive forces development and the major social and political transformations resulted in qualitative changes in the processes of international labor migration. At the same time in the context of globalization the place and role of international labor migration changes in the global economy system: migration becomes a means of promoting the globalization of countries and regions, the most important factor of demographic development and economic growth.

  14. Optimal initiation of electronic excited state mediated intramolecular H-transfer in malonaldehyde by UV-laser pulses

    Science.gov (United States)

    Nandipati, K. R.; Singh, H.; Nagaprasad Reddy, S.; Kumar, K. A.; Mahapatra, S.

    2014-12-01

    Optimally controlled initiation of intramolecular H-transfer in malonaldehyde is accomplished by designing a sequence of ultrashort (~80 fs) down-chirped pump-dump ultra violet (UV)-laser pulses through an optically bright electronic excited [ S 2 ( π π ∗)] state as a mediator. The sequence of such laser pulses is theoretically synthesized within the framework of optimal control theory (OCT) and employing the well-known pump-dump scheme of Tannor and Rice [D.J. Tannor, S.A. Rice, J. Chem. Phys. 83, 5013 (1985)]. In the OCT, the control task is framed as the maximization of cost functional defined in terms of an objective function along with the constraints on the field intensity and system dynamics. The latter is monitored by solving the time-dependent Schrödinger equation. The initial guess, laser driven dynamics and the optimized pulse structure (i.e., the spectral content and temporal profile) followed by associated mechanism involved in fulfilling the control task are examined in detail and discussed. A comparative account of the dynamical outcomes within the Condon approximation for the transition dipole moment versus its more realistic value calculated ab initio is also presented.

  15. Benzothiazole-Based AIEgen with Tunable Excited-State Intramolecular Proton Transfer and Restricted Intramolecular Rotation Processes for Highly Sensitive Physiological pH Sensing.

    Science.gov (United States)

    Li, Kai; Feng, Qi; Niu, Guangle; Zhang, Weijie; Li, Yuanyuan; Kang, Miaomiao; Xu, Kui; He, Juan; Hou, Hongwei; Tang, Ben Zhong

    2018-04-23

    In this work, a benzothiazole-based aggregation-induced emission luminogen (AIEgen) of 2-(5-(4-carboxyphenyl)-2-hydroxyphenyl)benzothiazole (3) was designed and synthesized, which exhibited multifluorescence emissions in different dispersed or aggregated states based on tunable excited-state intramolecular proton transfer (ESIPT) and restricted intramolecular rotation (RIR) processes. 3 was successfully used as a ratiometric fluorescent chemosensor for the detection of pH, which exhibited reversible acid/base-switched yellow/cyan emission transition. More importantly, the pH jump of 3 was very precipitous from 7.0 to 8.0 with a midpoint of 7.5, which was well matched with the physiological pH. This feature makes 3 very suitable for the highly sensitive detection of pH fluctuation in biosamples and neutral water samples. 3 was also successfully used as a ratiometric fluorescence chemosensor for the detection of acidic and basic organic vapors in test papers.

  16. Intramolecular electron transfer in ascorbate oxidase is enhanced in the presence of oxygen

    DEFF Research Database (Denmark)

    Farver, O; Wherland, S; Pecht, I

    1994-01-01

    Intramolecular electron transfer from the type 1 copper center to the type 3 copper(II) pair is induced in the multi-copper enzyme, ascorbate oxidase, following pulse radiolytic reduction of the type 1 Cu(II) ion. In the presence of a slight excess of dioxygen over ascorbate oxidase, interaction...... between the trinuclear copper center and O2 is observed even with singly reduced ascorbate oxidase molecules. Under these conditions, the rate constant for intramolecular electron transfer from type 1 Cu(I) to type 3 Cu(II) increases 5-fold to 1100 +/- 300 s-1 (20 degrees C, pH 5.8) as compared...

  17. Synthesis of novel steroid-tetrahydroquinoline hybrid molecules and D-homosteroids by intramolecular cyclization reactions.

    Science.gov (United States)

    Magyar, Angéla; Wölfling, János; Kubas, Melanie; Cuesta Seijo, Jose Antonio; Sevvana, Madhumati; Herbst-Irmer, Regine; Forgó, Péter; Schneider, Gyula

    2004-05-01

    Steroidal aryliminium salts were prepared from D-seco-pregnene aldehyde 2b, and their BF3.OEt2-catalyzed reactions were studied. The nature of the substituent R1 in the anilines 3-6 essentially influenced the chemoselectivity. Using unsubstituted 3, 4-methoxy- (4) or 4-bromoaniline (5), different tetrahydroquinoline derivatives 7a-13a via intramolecular hetero Diels-Alder reaction were formed. In the case of 4-nitroaniline (6) the N-arylamino-D-homopregnane (14a) were also obtained. We assume, that an intramolecular Prins reaction led to this type of fluoro-D-homosteroid. The main products represent a new class of tetrahydroquinolino-androstenes.

  18. Neglected chaos in international stock markets: Bayesian analysis of the joint return-volatility dynamical system

    Science.gov (United States)

    Tsionas, Mike G.; Michaelides, Panayotis G.

    2017-09-01

    We use a novel Bayesian inference procedure for the Lyapunov exponent in the dynamical system of returns and their unobserved volatility. In the dynamical system, computation of largest Lyapunov exponent by traditional methods is impossible as the stochastic nature has to be taken explicitly into account due to unobserved volatility. We apply the new techniques to daily stock return data for a group of six countries, namely USA, UK, Switzerland, Netherlands, Germany and France, from 2003 to 2014, by means of Sequential Monte Carlo for Bayesian inference. The evidence points to the direction that there is indeed noisy chaos both before and after the recent financial crisis. However, when a much simpler model is examined where the interaction between returns and volatility is not taken into consideration jointly, the hypothesis of chaotic dynamics does not receive much support by the data ("neglected chaos").

  19. International conference on dynamical systems and game theory in honor of Mauricio Peixoto and David Rand

    CERN Document Server

    Peixoto, Mauricio Matos; Rand, David A J; Dynamics, Games and Science I

    2011-01-01

    "Dynamics, Games and Science I and II" are a selection of surveys and research articles written by leading researchers in mathematics and its applications to the sciences. The majority of the contributions are on dynamical systems and game theory, focusing either on some of their most fundamental and theoretical developments or on their applications to modeling in biology, economics, engineering, finances and psychology. The aim of these books is to present cutting-edge research in these areas that can encourage graduate students and researchers in mathematics to develop them further

  20. Glitches as probes of neutron star internal structure and dynamics: Effects of the superfluid-superconducting core

    Science.gov (United States)

    Gügercinoğlu, Erbil

    2017-12-01

    Glitches, sudden spin-up of pulsars with subsequent recovery, provide us with a unique opportunity to investigate various physical processes, including the crust-core coupling, distribution of reservoir angular momentum within different internal layers, spin-up in neutral and charged superfluids and constraining the equation of state of the neutron star (NS) matter. In this work, depending on the dynamic interaction between the vortex lines and the nuclei in the inner crust, and between the vortex lines and the magnetic flux tubes in the outer core, various types of relaxation behavior are obtained and confronted with the observations. It is shown that the glitches have strong potential to deduce information about the cooling behavior and interior magnetic field configuration of NSs. Some implications of the relative importance of the external spin-down torques and the superfluid internal torques for recently observed unusual glitches are also discussed.

  1. Dynamic functional coupling of high resolution EEG potentials related to unilateral internally triggered one-digit movements.

    Science.gov (United States)

    Urbano, A; Babiloni, C; Onorati, P; Babiloni, F

    1998-06-01

    Between-electrode cross-covariances of delta (0-3 Hz)- and theta (4-7 Hz)-filtered high resolution EEG potentials related to preparation, initiation. and execution of human unilateral internally triggered one-digit movements were computed to investigate statistical dynamic coupling between these potentials. Significant (P planning, starting, and performance of unilateral movement. The involvement of these cortical areas is supported by the observation that averaged spatially enhanced delta- and theta-bandpassed potentials were computed from the scalp regions where task-related electrical activation of primary sensorimotor areas and supplementary motor area was roughly represented.

  2. Pectins, Hemicelluloses and Celluloses Show Specific Dynamics in the Internal and External Surfaces of Grape Berry Skin During Ripening.

    Science.gov (United States)

    Fasoli, Marianna; Dell'Anna, Rossana; Dal Santo, Silvia; Balestrini, Raffaella; Sanson, Andrea; Pezzotti, Mario; Monti, Francesca; Zenoni, Sara

    2016-06-01

    Grapevine berry skin is a complex structure that contributes to the final size and shape of the fruit and affects its quality traits. The organization of cell wall polysaccharides in situ and their modification during ripening are largely uncharacterized. The polymer structure of Corvina berry skin, its evolution during ripening and related modifying genes were determined by combing mid-infrared micro-spectroscopy and multivariate statistical analysis with transcript profiling and immunohistochemistry. Spectra were acquired in situ using a surface-sensitive technique on internal and external sides of the skin without previous sample pre-treatment, allowing comparison of the related cell wall polymer dynamics. The external surface featured cuticle-related bands; the internal surface showed more adsorbed water. Application of surface-specific normalization revealed the major molecular changes related to hemicelluloses and pectins in the internal surface and to cellulose and pectins in the external surface and that they occur between mid-ripening and full ripening in both sides of the skin. Transcript profiling of cell wall-modifying genes indicated a general suppression of cell wall metabolism during ripening. Genes related to pectin metabolism-a β-galactosidase, a pectin(methyl)esterase and a pectate lyase-and a xyloglucan endotransglucosylase/hydrolase, involved in hemicellulose modification, showed enhanced expression. In agreement with Fourier transform infrared spectroscopy, patterns due to pectin methyl esterification provided new insights into the relationship between pectin modifications and the associated transcript profile during skin ripening. This study proposes an original description of polymer dynamics in grape berries during ripening, highlighting differences between the internal and external sides of the skin. © The Author 2016. Published by Oxford University Press on behalf of Japanese Society of Plant Physiologists. All rights reserved. For

  3. The world network of scientific collaborations between cities: domestic or international dynamics?

    Energy Technology Data Exchange (ETDEWEB)

    Maisonobe, M.; Eckert, D.; Grossetti, M.; Jégou, L.; Milard, B.

    2016-07-01

    Earlier publication (Grossetti et al., 2014) has established that we are attending a decreasing concentration of scientific activities within “world-cities”. Given that more and more cities and countries are contributing to the world production of knowledge, this article analyzes the evolution of the world network of collaborations both at the domestic and international levels during the 2000s. Using data from the Science Citation Index Expanded, scientific authors’ addresses are geo-localized and grouped by urban areas. Our data suggests that interurban collaborations within countries have increased together with international linkages. In most countries, domestic collaborations have increased faster than international collaborations. Even among the top collaborating cities, sometimes referred to as “world cities”, the share of domestic collaborations is gaining momentum. Our results suggest that, contrary to common beliefs about the globalization process, national systems of research have been strengthening during the 2000s. (Author)

  4. The dynamics of tax havens: An analysis from an international and domestic perspective

    OpenAIRE

    Kolade, Deborah

    2017-01-01

    2017 dissertation for Master of Law in International Business Law. Selected by academic staff as a good example of a masters level dissertation. Since the occurrence of history’s biggest data leak known as Panama Papers, more\\ud focus has been placed upon offshore dealings and tax havens. With no clear\\ud definition on what tax haven is, this research will be exploring the usage of tax\\ud haven internationally whilst paying particular attention to the United Kingdom,\\ud it’s perspectives and ...

  5. Internal sub-sonic burning during an explosion viewed via dynamic X-ray radiography

    Science.gov (United States)

    Smilowitz, L.; Henson, B. F.; Oschwald, D.; Suvorova, N.; Remelius, D.

    2017-10-01

    We observe internal convective and conductive burn front propagation and solid consumption subsequent to thermal ignition for plastic bonded formulations of the solid organic secondary explosives octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine and 1,3,5-triamino-2,4,6-trinitrobenzene. This work describes x-ray radiographic diagnostics enabling the study of solid density in a fully encased explosive during internal burning subsequent to ignition. The result of this study is the ability to directly observe and measure rates of energy release during a thermal explosion.

  6. Rule of Law Dynamics in an Era of International and Transnational Governance

    NARCIS (Netherlands)

    Zürn, M.; Nollkaemper, A.; Peerenboom, R.

    2011-01-01

    The international and transnational nature of modern governance presents major challenges for the rule of law promotion agenda, at a time when the less than stellar results of traditional state-oriented rule of law promotion have led to increased doubts about the wisdom and feasibility of the

  7. Dynamism and the erosion of procedural safeguards in international governance of terrorism

    NARCIS (Netherlands)

    N.T. Ali (Nathanael)

    2015-01-01

    markdownabstractAbstract Contemporary international governance of terrorism reflects a conceptualisation of terrorism as a global public problem that both affects and needs to be responded to by all sectors of global society. Consequently, counter-terrorism has taken the form of proactive risk

  8. Analysis of Leadership Dynamics in Educational Settings during Times of External and Internal Change

    Science.gov (United States)

    Jäppinen, Aini-Kristiina

    2017-01-01

    Background: The article concerns the tensions that can arise during demanding external, and consequential internal changes and considers how educational leadership is able to respond to them. Leadership is here understood as a collaborative endeavour, producing shared sense-making in situations of tension. Purpose: The main research question was:…

  9. DREISS: Using State-Space Models to Infer the Dynamics of Gene Expression Driven by External and Internal Regulatory Networks

    Science.gov (United States)

    Gerstein, Mark

    2016-01-01

    Gene expression is controlled by the combinatorial effects of regulatory factors from different biological subsystems such as general transcription factors (TFs), cellular growth factors and microRNAs. A subsystem’s gene expression may be controlled by its internal regulatory factors, exclusively, or by external subsystems, or by both. It is thus useful to distinguish the degree to which a subsystem is regulated internally or externally–e.g., how non-conserved, species-specific TFs affect the expression of conserved, cross-species genes during evolution. We developed a computational method (DREISS, dreiss.gerteinlab.org) for analyzing the Dynamics of gene expression driven by Regulatory networks, both External and Internal based on State Space models. Given a subsystem, the “state” and “control” in the model refer to its own (internal) and another subsystem’s (external) gene expression levels. The state at a given time is determined by the state and control at a previous time. Because typical time-series data do not have enough samples to fully estimate the model’s parameters, DREISS uses dimensionality reduction, and identifies canonical temporal expression trajectories (e.g., degradation, growth and oscillation) representing the regulatory effects emanating from various subsystems. To demonstrate capabilities of DREISS, we study the regulatory effects of evolutionarily conserved vs. divergent TFs across distant species. In particular, we applied DREISS to the time-series gene expression datasets of C. elegans and D. melanogaster during their embryonic development. We analyzed the expression dynamics of the conserved, orthologous genes (orthologs), seeing the degree to which these can be accounted for by orthologous (internal) versus species-specific (external) TFs. We found that between two species, the orthologs have matched, internally driven expression patterns but very different externally driven ones. This is particularly true for genes with

  10. DREISS: Using State-Space Models to Infer the Dynamics of Gene Expression Driven by External and Internal Regulatory Networks.

    Directory of Open Access Journals (Sweden)

    Daifeng Wang

    2016-10-01

    Full Text Available Gene expression is controlled by the combinatorial effects of regulatory factors from different biological subsystems such as general transcription factors (TFs, cellular growth factors and microRNAs. A subsystem's gene expression may be controlled by its internal regulatory factors, exclusively, or by external subsystems, or by both. It is thus useful to distinguish the degree to which a subsystem is regulated internally or externally-e.g., how non-conserved, species-specific TFs affect the expression of conserved, cross-species genes during evolution. We developed a computational method (DREISS, dreiss.gerteinlab.org for analyzing the Dynamics of gene expression driven by Regulatory networks, both External and Internal based on State Space models. Given a subsystem, the "state" and "control" in the model refer to its own (internal and another subsystem's (external gene expression levels. The state at a given time is determined by the state and control at a previous time. Because typical time-series data do not have enough samples to fully estimate the model's parameters, DREISS uses dimensionality reduction, and identifies canonical temporal expression trajectories (e.g., degradation, growth and oscillation representing the regulatory effects emanating from various subsystems. To demonstrate capabilities of DREISS, we study the regulatory effects of evolutionarily conserved vs. divergent TFs across distant species. In particular, we applied DREISS to the time-series gene expression datasets of C. elegans and D. melanogaster during their embryonic development. We analyzed the expression dynamics of the conserved, orthologous genes (orthologs, seeing the degree to which these can be accounted for by orthologous (internal versus species-specific (external TFs. We found that between two species, the orthologs have matched, internally driven expression patterns but very different externally driven ones. This is particularly true for genes with

  11. The dynamic interaction between combustible renewables and waste consumption and international tourism: the case of Tunisia.

    Science.gov (United States)

    Ben Jebli, Mehdi; Ben Youssef, Slim; Apergis, Nicholas

    2015-08-01

    This paper employs the autoregressive distributed lag (ARDL) bounds methodological approach to investigate the relationship between economic growth, combustible renewables and waste consumption, carbon dioxide (CO2) emissions, and international tourism for the case of Tunisia spanning the period 1990-2010. The results from the Fisher statistic of both the Wald test and the Johansen test confirm the presence of a long-run relationship among the variables under investigation. The stability of estimated parameters has been tested, while Granger causality tests recommend a short-run unidirectional causality running from economic growth and combustible renewables and waste consumption to CO2 emissions, a bidirectional causality between economic growth and combustible renewables and waste consumption and unidirectional causality running from economic growth and combustible renewables and waste consumption to international tourism. In the long-run, the error correction terms confirm the presence of bidirectional causality relationships between economic growth, CO2 emissions, combustible renewables and waste consumption, and international tourism. Our long-run estimates show that combustible renewables and waste consumption increases international tourism, and both renewables and waste consumption and international tourism increase CO2 emissions and output. We recommend that (i) Tunisia should use more combustible renewables and waste energy as this eliminates wastes from touristic zones and increases the number of tourist arrivals, leading to economic growth, and (ii) a fraction of this economic growth generated by the increase in combustible renewables and waste consumption should be invested in clean renewable energy production (i.e., solar, wind, geothermal) and energy efficiency projects.

  12. Effects of changes in nutrient loading and composition on hypoxia dynamics and internal nutrient cycling of a stratified coastal lagoon

    Science.gov (United States)

    Zhu, Yafei; McCowan, Andrew; Cook, Perran L. M.

    2017-10-01

    The effects of changes in catchment nutrient loading and composition on the phytoplankton dynamics, development of hypoxia and internal nutrient dynamics in a stratified coastal lagoon system (the Gippsland Lakes) were investigated using a 3-D coupled hydrodynamic biogeochemical water quality model. The study showed that primary production was equally sensitive to changed dissolved inorganic and particulate organic nitrogen loads, highlighting the need for a better understanding of particulate organic matter bioavailability. Stratification and sediment carbon enrichment were the main drivers for the hypoxia and subsequent sediment phosphorus release in Lake King. High primary production stimulated by large nitrogen loading brought on by a winter flood contributed almost all the sediment carbon deposition (as opposed to catchment loads), which was ultimately responsible for summer bottom-water hypoxia. Interestingly, internal recycling of phosphorus was more sensitive to changed nitrogen loads than total phosphorus loads, highlighting the potential importance of nitrogen loads exerting a control over systems that become phosphorus limited (such as during summer nitrogen-fixing blooms of cyanobacteria). Therefore, the current study highlighted the need to reduce both total nitrogen and total phosphorus for water quality improvement in estuarine systems.

  13. Effects of changes in nutrient loading and composition on hypoxia dynamics and internal nutrient cycling of a stratified coastal lagoon

    Directory of Open Access Journals (Sweden)

    Y. Zhu

    2017-10-01

    Full Text Available The effects of changes in catchment nutrient loading and composition on the phytoplankton dynamics, development of hypoxia and internal nutrient dynamics in a stratified coastal lagoon system (the Gippsland Lakes were investigated using a 3-D coupled hydrodynamic biogeochemical water quality model. The study showed that primary production was equally sensitive to changed dissolved inorganic and particulate organic nitrogen loads, highlighting the need for a better understanding of particulate organic matter bioavailability. Stratification and sediment carbon enrichment were the main drivers for the hypoxia and subsequent sediment phosphorus release in Lake King. High primary production stimulated by large nitrogen loading brought on by a winter flood contributed almost all the sediment carbon deposition (as opposed to catchment loads, which was ultimately responsible for summer bottom-water hypoxia. Interestingly, internal recycling of phosphorus was more sensitive to changed nitrogen loads than total phosphorus loads, highlighting the potential importance of nitrogen loads exerting a control over systems that become phosphorus limited (such as during summer nitrogen-fixing blooms of cyanobacteria. Therefore, the current study highlighted the need to reduce both total nitrogen and total phosphorus for water quality improvement in estuarine systems.

  14. Internal Migration, Regional Labour Market Dynamics and Implications for German East-West Disparities – Results from a Panel VAR

    DEFF Research Database (Denmark)

    Alecke, Björn; Mitze, Timo; Untiedt, Gerhard

    This paper analyses the causal linkages between regional labour market variables and internal migration flows among German states between 1991–2006. We adopt a Panel VAR approach to identify the feedback effects among the variables and analyse the dynamic properties of the system through impulser......This paper analyses the causal linkages between regional labour market variables and internal migration flows among German states between 1991–2006. We adopt a Panel VAR approach to identify the feedback effects among the variables and analyse the dynamic properties of the system through...... impulseresponse functions.We also use the model to track the evolution of the particular East-West migration since re-unification aiming to shed more light on the East German “empirical puzzle”, characterized by lower migration responses than expected from the regional labour market position relative to the West......:That is, along with a second wave of East-West movements around 2001 net flows out of East Germany were much higher than expected after controlling for its weak labour market and macroeconomic performance. Since this second wave is also accompanied by a gradual fading out of economic distortions...

  15. Evaluation of Internal Friction versus Plastic Deformations Effects in Impact Dynamics Problems of Robotic Elements

    Directory of Open Access Journals (Sweden)

    Stelian Alaci

    2014-06-01

    Full Text Available The dynamical behavior study of robotic systems is obtained using multibody dynamics method. The joints met in robots are modeled in different manners. In a robotic joint the energy is lost via hysteretic work and plastic deformation work. The paper presents a comparative study for the results obtained by integration of the equations defining two limit models which describe the impact between two robot parts, modeled by the centric collision between two spheres with loss of energy. The motion equations characteristic for the two models are integrated and for a tangible situation, are presented comparatively, for different values of the coefficient of restitution, the time dependencies of impacting force between the two bodies as well as the hysteresis loops. Finally, an evaluation of the lost work during impact, for the whole range of coefficients of restitution, is completed, together with characteristic parameters of collision: approaching period, complete contact time, maximum approaching and plastic imprint.

  16. Exhaust Gas Temperature Measurements in Diagnostics of Turbocharged Marine Internal Combustion Engines Part II Dynamic Measurements

    Directory of Open Access Journals (Sweden)

    Korczewski Zbigniew

    2016-01-01

    Full Text Available The second part of the article describes the technology of marine engine diagnostics making use of dynamic measurements of the exhaust gas temperature. Little-known achievements of Prof. S. Rutkowski of the Naval College in Gdynia (now: Polish Naval Academy in this area are presented. A novel approach is proposed which consists in the use of the measured exhaust gas temperature dynamics for qualitative and quantitative assessment of the enthalpy flux of successive pressure pulses of the exhaust gas supplying the marine engine turbocompressor. General design assumptions are presented for the measuring and diagnostic system which makes use of a sheathed thermocouple installed in the engine exhaust gas manifold. The corrected thermal inertia of the thermocouple enables to reproduce a real time-history of exhaust gas temperature changes.

  17. Structural criteria for extreme dynamic internal pressure loadings of vessels and closure heads

    International Nuclear Information System (INIS)

    Bitner, J.L.

    1985-01-01

    The criteria protect against tensile plastic instability and local ductile rupture failure modes. To minimize the number of critical areas that may need more rigorous analytical methods, a screening criterion for limiting the membrane, bending and local stresses is defined. The stresses for this criterion are calculated from either simple and economical elastic dynamic or equivalent static methods. For the critical areas that remain, a strain-based criterion for strains derived from dynamic, inelastic methods is given. To assure that the criteria are properly applied, guidelines are outlined for controlling methods for deriving stresses and strains, for selecting appropriate material properties and for addressing specific dominating parameters that affect the validity of the analysis. The application of the criteria to a complex liquid metal fast breeder reactor vessel and closure head and the subsequent experimental verification of the results by several scale model experiments are summarized. (orig./HP)

  18. On the internal stability of non-linear dynamic inversion: application to flight control

    Czech Academy of Sciences Publication Activity Database

    Alam, M.; Čelikovský, Sergej

    2017-01-01

    Roč. 11, č. 12 (2017), s. 1849-1861 ISSN 1751-8644 R&D Projects: GA ČR(CZ) GA17-04682S Institutional support: RVO:67985556 Keywords : flight control * non-linear dynamic inversion * stability Subject RIV: BC - Control Systems Theory OBOR OECD: Automation and control systems Impact factor: 2.536, year: 2016 http://library.utia.cas.cz/separaty/2017/TR/celikovsky-0476150.pdf

  19. A Dynamic Model of Internally-Driven Corporate Social Responsibility and Enlightened Profit Maximization

    OpenAIRE

    F. Balboni

    2009-01-01

    The aim of this paper is to contribute to the analysis of Corporate Social Responsibility (CSR) from an economic perspective, in two ways. Firstly, introducing a new definition and a new framework of analysis, which can account for both the externallydriven and the internallydriven view of CSR. Secondly, developing a dynamic model of internallydriven CSR – which draws inspiration from the literature on renewable resources – to show that, under certain circumstances, an enlightened profit‐maxi...

  20. Markov switching mean-variance frontier dynamics: theory and international evidence

    OpenAIRE

    M. Guidolin; F. Ria

    2010-01-01

    It is well-known that regime switching models are able to capture the presence of rich non-linear patterns in the joint distribution of asset returns. After reviewing key concepts and technical issues related to specifying, estimating, and using multivariate Markov switching models in financial applications, in this paper we map the presence of regimes in means, variances, and covariances of asset returns into explicit dynamics of the Markowitz mean-variance frontier. In particular, we show b...

  1. Global-scale equatorial Rossby waves as an essential component of solar internal dynamics

    Science.gov (United States)

    Löptien, Björn; Gizon, Laurent; Birch, Aaron C.; Schou, Jesper; Proxauf, Bastian; Duvall, Thomas L.; Bogart, Richard S.; Christensen, Ulrich R.

    2018-05-01

    The Sun’s complex dynamics is controlled by buoyancy and rotation in the convection zone. Large-scale flows are dominated by vortical motions1 and appear to be weaker than expected in the solar interior2. One possibility is that waves of vorticity due to the Coriolis force, known as Rossby waves3 or r modes4, remove energy from convection at the largest scales5. However, the presence of these waves in the Sun is still debated. Here, we unambiguously discover and characterize retrograde-propagating vorticity waves in the shallow subsurface layers of the Sun at azimuthal wavenumbers below 15, with the dispersion relation of textbook sectoral Rossby waves. The waves have lifetimes of several months, well-defined mode frequencies below twice the solar rotational frequency, and eigenfunctions of vorticity that peak at the equator. Rossby waves have nearly as much vorticity as the convection at the same scales, thus they are an essential component of solar dynamics. We observe a transition from turbulence-like to wave-like dynamics around the Rhines scale6 of angular wavenumber of approximately 20. This transition might provide an explanation for the puzzling deficit of kinetic energy at the largest spatial scales.

  2. A simple and versatile design concept for fluorophore derivatives with intramolecular photostabilization

    NARCIS (Netherlands)

    van der Velde, Jasper H M; Oelerich, Jens; Huang, Jingyi; Smit, Jochem H; Aminian Jazi, Atieh; Galiani, Silvia; Kolmakov, Kirill; Guoridis, Giorgos; Eggeling, Christian; Herrmann, Andreas; Roelfes, Gerard; Cordes, Thorben

    2016-01-01

    Intramolecular photostabilization via triple-state quenching was recently revived as a tool to impart synthetic organic fluorophores with 'self-healing' properties. To date, utilization of such fluorophore derivatives is rare due to their elaborate multi-step synthesis. Here we present a general

  3. Long-range intramolecular electron transfer in aromatic radical anions and binuclear transition metal complexes

    DEFF Research Database (Denmark)

    Kuznetsov, A. M.; Ulstrup, Jens

    1981-01-01

    Intramolecular electron transfer (ET) over distances up to about 10 Å between states in which the electron is localized on donor and acceptor groups by interaction with molecular or external solvent nuclear motion occurs, in particular, in two classes of systems. The excess electron in anionic ra...

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

    DEFF Research Database (Denmark)

    Juhl, M.; Tanner, David Ackland

    2009-01-01

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

  5. Intramolecular Diels-Alder reactions of pyrimidines, a synthetic and computational study

    NARCIS (Netherlands)

    Stolle, W.A.W.

    1992-01-01

    This thesis deals with an investigation on the ringtransformation reactions of 2and 5-(ω-alkynyl)pyrimidine derivatives, which undergo upon heating an intramolecular Diels-Alder reaction and subsequently a spontaneous retro Diels- Alder reaction. To get a better insight into the

  6. Optimized measurements of separations and angles between intra-molecular fluorescent markers

    DEFF Research Database (Denmark)

    Mortensen, Kim; Sung, Jongmin; Flyvbjerg, Henrik

    2015-01-01

    We demonstrate a novel, yet simple tool for the study of structure and function of biomolecules by extending two-colour co-localization microscopy to fluorescent molecules with fixed orientations and in intra-molecular proximity. From each colour-separated microscope image in a time-lapse movie...

  7. Potassium hydroxide/dimethyl sulfoxide promoted intramolecular cyclization for the synthesis of benzimidazol-2-ones.

    Science.gov (United States)

    Beyer, Astrid; Reucher, Christine M M; Bolm, Carsten

    2011-06-03

    A new protocol for intramolecular N-arylations of ureas to form benzimidazol-2-ones has been developed. The cyclization reaction occurs in the presence of KOH and DMSO at close to ambient temperature. Under these conditions the yields are high and a wide range of functional groups are tolerated.

  8. On prediction of OH stretching frequencies in intramolecularly hydrogen bonded systems

    DEFF Research Database (Denmark)

    Hansen, Poul Erik; Spanget-Larsen, Jens

    2012-01-01

    OH stretching frequencies are investigated for a series of non-tautomerizing systems with intramolecular hydrogen bonds. Effective OH stretching wavenumbers are predicted by the application of empirical correlation procedures based on the results of B3LYP/6-31G(d) theoretical calculations...

  9. Chemical synthesis of dual labeled proteins via differently protected alkynes enables intramolecular FRET analysis.

    Science.gov (United States)

    Hayashi, Gosuke; Kamo, Naoki; Okamoto, Akimitsu

    2017-05-30

    We report a novel method for multisite protein conjugation by setting differently silyl-protected alkynes as conjugation handles, which can remain intact through the whole synthetic procedure and provide sequential and orthogonal conjugation. This strategy enables efficient preparation of a dual dye-labeled protein and structural analysis via an intramolecular FRET mechanism.

  10. Thermal and catalytic intramolecular [4+2]-cycloaddition in 2-alkenylfurans

    International Nuclear Information System (INIS)

    Zubkov, Fedor I; Nikitina, Evgenia V; Varlamov, Alexey V

    2005-01-01

    The published data on the intramolecular Diels-Alder reaction in compounds of the 2-alkenylfuran series are generalised. The methods and conditions for the preparation of tricyclic systems are considered. The effects of the substituents in the furan and the unsaturated fragments on the cycloaddition are discussed. The application of this reaction to the synthesis of alkaloids and terpenoids is exemplified.

  11. Synthesis of benzannelated sultams by intramolecular Pd-catalyzed arylation of tertiary sulfonamides

    Directory of Open Access Journals (Sweden)

    Valentin A. Rassadin

    2017-09-01

    Full Text Available A new and efficient approach to five- and six-membered benzannelated sultams by intramolecular C-arylation of tertiary 1-(methoxycarbonylmethanesulfonamides under palladium catalysis is described. In case of the α-toluenesulfonamide derivative, an unexpected formation of a 2,3-diarylindole was observed under the same conditions.

  12. A novel stereoselective synthesis of N-heterocycles by intramolecular hydrovinylation

    DEFF Research Database (Denmark)

    Bothe, Ulrich; Rudbeck, H. C.; Tanner, David Ackland

    2001-01-01

    A novel method for the synthesis of bicyclic amines has been developed. Cyclisation of 1,6-dienes by intramolecular hydrovinylation in the presence of catalytic amounts of allylpalladium chloride dimer afforded bicyclic amines in one step. Added phosphines, silver salts, as well as the nature of ...

  13. Thermal and catalytic intramolecular [4+2]-cycloaddition in 2-alkenylfurans

    Energy Technology Data Exchange (ETDEWEB)

    Zubkov, Fedor I; Nikitina, Evgenia V; Varlamov, Alexey V [Department of Physical, Mathematical and Natural Sciences, Peoples' Friendship University of Russia (Russian Federation)

    2005-07-31

    The published data on the intramolecular Diels-Alder reaction in compounds of the 2-alkenylfuran series are generalised. The methods and conditions for the preparation of tricyclic systems are considered. The effects of the substituents in the furan and the unsaturated fragments on the cycloaddition are discussed. The application of this reaction to the synthesis of alkaloids and terpenoids is exemplified.

  14. Symmetry-breaking intramolecular charge transfer in the excited state of meso-linked BODIPY dyads

    KAUST Repository

    Whited, Matthew T.; Patel, Niral M.; Roberts, Sean T.; Allen, Kathryn; Djurovich, Peter I.; Bradforth, Stephen E.; Thompson, Mark E.

    2012-01-01

    We report the synthesis and characterization of symmetric BODIPY dyads where the chromophores are attached at the meso position, using either a phenylene bridge or direct linkage. Both molecules undergo symmetry-breaking intramolecular charge transfer in the excited state, and the directly linked dyad serves as a visible-light-absorbing analogue of 9,9′-bianthryl.

  15. Intramolecular excimer and exciplex emission of 1,4-dipyrenyl substituted cyclohexasilane

    NARCIS (Netherlands)

    van Walree, C.A.; Kaats-Richters, V.E.M.; Jenneskens, L.W.; Williams, R.M.; van Stokkum, I.H.M.

    2002-01-01

    Intramolecular excimer emission is observed for cis-1,4-di(1-pyrenyl)decamethylcyclohexasilane in nonpolar solvents. Time-resolved fluorescence spectroscopy and kinetic modelling indicate that the driving force of excimer formation is very small, and that the process is governed by the flexibility

  16. Effect of intramolecular hydrogen bonding and electron donation on substituted anthrasemiquinone characteristics

    International Nuclear Information System (INIS)

    Pal, H.; Mukherjee, T.

    1994-01-01

    The acid-base and redox characteristics of the semiquinones of a number of hydroxy and amino-substituted anthraquinones have been investigated. Results are explained on the basis of electron-donating properties and intramolecular hydrogen bond forming capabilities of the substituents. (author). 4 refs., 1 tab., 1 fig

  17. Rapid examination of the kinetic process of intramolecular lactamization of gabapentin using DSC-FTIR

    International Nuclear Information System (INIS)

    Hsu, C.-H.; Lin, S.-Y.

    2009-01-01

    The thermal stability and thermodynamics of gabapentin (GBP) in the solid state were investigated by DSC and TG techniques, and FTIR microspectroscopy. The detailed intramolecular lactamization process of GBP to form gabapentin-lactam (GBP-L) was also determined by thermal FTIR microspectroscopy. GBP exhibited a DSC endothermic peak at 169 deg. C. The weight loss in TG curve of GBP suggested that the evaporation process of water liberated via intramolecular lactamization was simultaneously combined with the evaporation process of GBP-L having a DSC endothermic peak at 91 deg. C. A thermal FTIR microspectroscopy clearly evidenced the IR spectra at 3350 cm -1 for water liberated and at 1701 cm -1 for lactam structure formed due to the lactam formation of GBP. This study indicates that the activation energy for combined processes of intramolecular lactamization of GBP and evaporation of GBP-L was about 114.3 ± 23.3 kJ/mol, but for the evaporation of GBP-L alone was 76.2 ± 1.5 kJ/mol. A powerful simultaneous DSC-FTIR combined technique was easily used to quickly examine the detailed kinetic processes of intramolecular cyclization of GPB and evaporation of GBP-L in the solid state

  18. The spatiotemporal dynamic analysis of the implied market information and characteristics of the correlation coefficient matrix of the international crude oil price returns

    International Nuclear Information System (INIS)

    Tian, Lixin; Ding, Zhenqi; Zhen, Zaili; Wang, Minggang

    2016-01-01

    The international crude oil market plays a crucial role in economies, and the studies of the correlation, risk and synchronization of the international crude oil market have important implications for the security and stability of the country, avoidance of business risk and people's daily lives. We investigate the information and characteristics of the international crude oil market (1999-2015) based on the random matrix theory (RMT). Firstly, we identify richer information in the largest eigenvalues deviating from RMT predictions for the international crude oil market; the international crude oil market can be roughly divided into ten different periods by the methods of eigenvectors and characteristic combination, and the implied market information of the correlation coefficient matrix is advanced. Secondly, we study the characteristics of the international crude oil market by the methods of system risk entropy, dynamic synchronous ratio, dynamic non-synchronous ratio and dynamic clustering algorithm. The results show that the international crude oil market is full of risk. The synchronization of the international crude oil market is very strong, and WTI and Brent occupy a very important position in the international crude oil market. (orig.)

  19. The spatiotemporal dynamic analysis of the implied market information and characteristics of the correlation coefficient matrix of the international crude oil price returns

    Energy Technology Data Exchange (ETDEWEB)

    Tian, Lixin [Jiangsu University, Energy Development and Environmental Protection Strategy Research Center, Zhenjiang, Jiangsu (China); Nanjing Normal University, School of Mathematical Sciences, Nanjing, Jiangsu (China); Ding, Zhenqi; Zhen, Zaili [Jiangsu University, Energy Development and Environmental Protection Strategy Research Center, Zhenjiang, Jiangsu (China); Wang, Minggang [Nanjing Normal University, School of Mathematical Sciences, Nanjing, Jiangsu (China)

    2016-08-15

    The international crude oil market plays a crucial role in economies, and the studies of the correlation, risk and synchronization of the international crude oil market have important implications for the security and stability of the country, avoidance of business risk and people's daily lives. We investigate the information and characteristics of the international crude oil market (1999-2015) based on the random matrix theory (RMT). Firstly, we identify richer information in the largest eigenvalues deviating from RMT predictions for the international crude oil market; the international crude oil market can be roughly divided into ten different periods by the methods of eigenvectors and characteristic combination, and the implied market information of the correlation coefficient matrix is advanced. Secondly, we study the characteristics of the international crude oil market by the methods of system risk entropy, dynamic synchronous ratio, dynamic non-synchronous ratio and dynamic clustering algorithm. The results show that the international crude oil market is full of risk. The synchronization of the international crude oil market is very strong, and WTI and Brent occupy a very important position in the international crude oil market. (orig.)

  20. 'Wildlife 2001: Populations', an International Conference on Population Dynamics and Management of Vertebrates

    CERN Document Server

    Barrett, Reginald

    1992-01-01

    In 1984, a conference called Wildlife 2000: Modeling habitat relationships of terrestrial vertebrates, was held at Stanford Sierra Camp at Fallen Leaf Lake in the Sierra Nevada Mountains of California. The conference was well-received, and the published volume (Verner, J. , M. L. Morrison, and C. J. Ralph, editors. 1986. Wildlife 2000: modeling habitat relationships of terrestrial vertebrates, University of Wisconsin Press, Madison, Wisconsin, USA) proved to be a landmark publication that received a book award by The Wildlife Society. Wildlife 2001: populations was a followup conference with emphasis on the other major biological field of wildlife conservation and management, populations. It was held on July 29-31, 1991, at the Oakland Airport Hilton Hotel in Oakland, California, in accordance with our intent that this conference have a much stronger international representation than did Wildlife 2000. The goal of the conference was to bring together an international group of specialists to address the state ...

  1. Dynamic characterization of external and internal mass transport in heterotrophic biofilms from microsensors measurements.

    Science.gov (United States)

    Guimerà, Xavier; Dorado, Antonio David; Bonsfills, Anna; Gabriel, Gemma; Gabriel, David; Gamisans, Xavier

    2016-10-01

    Knowledge of mass transport mechanisms in biofilm-based technologies such as biofilters is essential to improve bioreactors performance by preventing mass transport limitation. External and internal mass transport in biofilms was characterized in heterotrophic biofilms grown on a flat plate bioreactor. Mass transport resistance through the liquid-biofilm interphase and diffusion within biofilms were quantified by in situ measurements using microsensors with a high spatial resolution (mass transport coefficients. The sensitivity of external and internal mass transport resistances to flow conditions within the range of typical fluid velocities over biofilms (Reynolds numbers between 0.5 and 7) was assessed. Estimated external mass transfer coefficients at different liquid phase flow velocities showed discrepancies with studies considering laminar conditions in the diffusive boundary layer near the liquid-biofilm interphase. The correlation of effective diffusivity with flow velocities showed that the heterogeneous structure of biofilms defines the transport mechanisms inside biofilms. Internal mass transport was driven by diffusion through cell clusters and aggregates at Re below 2.8. Conversely, mass transport was driven by advection within pores, voids and water channels at Re above 5.6. Between both flow velocities, mass transport occurred by a combination of advection and diffusion. Effective diffusivities estimated at different biofilm densities showed a linear increase of mass transport resistance due to a porosity decrease up to biofilm densities of 50 g VSS·L(-1). Mass transport was strongly limited at higher biofilm densities. Internal mass transport results were used to propose an empirical correlation to assess the effective diffusivity within biofilms considering the influence of hydrodynamics and biofilm density. Copyright © 2016 Elsevier Ltd. All rights reserved.

  2. The dynamic interaction between combustible renewables and waste consumption and international tourism: The case of Tunisia

    OpenAIRE

    Ben Jebli, Mehdi; Ben Youssef, Slim; Apergis, Nicholas

    2014-01-01

    This paper employs the Autoregressive Distributed Lag (ARDL) bounds methodological approach to investigate the relationship between economic growth, combustible renewables and waste consumption, carbon dioxide (CO2) emissions and international tourism for the case of Tunisia spanning the period 1990-2010. The results from the Fisher statistic of both the Wald-test and the Johansen test confirm the presence of a long-run relationship among the variables under investigation. The stability of es...

  3. ANALYSING ROMANIAN INDUSTRIAL COMPETITIVENESS REGARDING THE RECENT DYNAMICS OF THE INTERNATIONAL INDUSTRIAL TRADE BALANCE

    OpenAIRE

    Felea Adrian Ioan

    2015-01-01

    The industry remains the most important sector of the national economy, although in the other member states the services have a more important share of GDP. In this context, the level of industrial competitiveness is essential for the national competitiveness. This is a characteristic feature for Romania, where the industry has an important share in the GDP, in comparison with the other member states. The international trade balance is an important indicator for measuring the economic competi...

  4. A dynamic approach to assess international competitiveness of Vietnam's garment and textile industry.

    Science.gov (United States)

    Vu, Huong Thanh; Pham, Lam Cat

    2016-01-01

    Garment and textile (G&T) industry has been playing as a driving force for the socio-economic development of Vietnam. With the international integration process and rising challenges from the global market, there is a need to examine international competitiveness of Vietnam's G&T industry to find out what Vietnam should focus on to enhance its position in the global market place. This paper, by using the Generalized Double Diamond Model (GDDM), analyzed international competitiveness of Vietnam's G&T industry and compared it with China. The results showed that Vietnam was less competitive than China in all four attributes of the GDDM. The lowest competitiveness of Vietnam in comparison with China was Related and Supporting industries, followed by Factor Conditions. Therefore, the paper argued that although Vietnam should improve all of the four attributes in the long term, Vietnam must put a high priority on developing Related and Supporting Industries and then enhance Factor Conditions while maintaining its strengths over China in terms of G&T export growths and favorable business context.

  5. NATO Advanced Study Institute on International Summer School on Chaotic Dynamics and Transport in Classical and Quantum Systems

    CERN Document Server

    Collet, P; Métens, S; Neishtadt, A; Zaslavsky, G; Chaotic Dynamics and Transport in Classical and Quantum Systems

    2005-01-01

    This book offers a modern updated review on the most important activities in today dynamical systems and statistical mechanics by some of the best experts in the domain. It gives a contemporary and pedagogical view on theories of classical and quantum chaos and complexity in hamiltonian and ergodic systems and their applications to anomalous transport in fluids, plasmas, oceans and atom-optic devices and to control of chaotic transport. The book is issued from lecture notes of the International Summer School on "Chaotic Dynamics and Transport in Classical and Quantum Systems" held in Cargèse (Corsica) 18th to the 30th August 2003. It reflects the spirit of the School to provide lectures at the post-doctoral level on basic concepts and tools. The first part concerns ergodicity and mixing, complexity and entropy functions, SRB measures, fractal dimensions and bifurcations in hamiltonian systems. Then, models of dynamical evolutions of transport processes in classical and quantum systems have been largely expla...

  6. Dynamics of seizure of animal products in international baggage on Airport of Brasilia (AIB-PJK/SBBR.

    Directory of Open Access Journals (Sweden)

    Cristiano Barros de Melo

    2016-09-01

    Full Text Available ABSTRACT. de Melo C.B., Fino T.C.M., Schwingel F.F., Santiago M.T., de Barros L.F.R., McManus C. & Sá M.E.P. [Dynamics of seizure of animal products in international baggage on Airport of Brasilia (AIB-PJK/SBBR.] Dinâmica da apreensão de produtos de origem animal em bagagens internacionais no Aeroporto de Brasília (AIB-PJK/SBBR. Revista Brasileira de Medicina Veterinária, 38(3:265-276, 2016. Universidade de Brasília, PPGCA, Campus Universitário Darcy Ribeiro, ICC Sul, Asa Norte, Brasília, DF 70910-900, Brasil. E-mail: cristianomelo@unb.br The risk of introducing infectious agents increases as the volume of imported products rises. The illegal entry of animal products (POA brought in international passenger baggage is a factor that makes up the risk assessment and that grows proportionally to the intensification of international transit passengers. They evaluated the data on seizures of animal products intercepted in international baggage passengers in Airport of Brasilia (AIB-PJK/SBBR between the years 2010 and 2012. The analysis of the dynamics of these seizures considered the POA category, origin, airline and months more frequently and also verified the correlation between these variables. According to retrospective analysis, nearly eight tons of POA were seized from 52 countries throughout the study period. The results showed Portugal (p <0.0001 as the source of passengers who had higher frequency and quantity of seizures, and, added to other European origins, totaled 84.3% of seizures. The months of July, August and September stood out for the highest number of seizures and greater movement of international passengers. The increase in the number of seizures accompanied by a rise in the percentage of inspected passengers (r=0.69, emphasizing the importance of airport surveillance. According to the calculation of relative risk, passengers from African and South American countries showed greater magnitude of risk to bring animal

  7. Kinematics and Dynamics Analysis of a 3-DOF Upper-Limb Exoskeleton with an Internally Rotated Elbow Joint

    Directory of Open Access Journals (Sweden)

    Xin Wang

    2018-03-01

    Full Text Available The contradiction between self-weight and load capacity of a power-assisted upper-limb exoskeleton for material hanging is unresolved. In this paper, a non-anthropomorphic 3-degree of freedom (DOF upper-limb exoskeleton with an internally rotated elbow joint is proposed based on an anthropomorphic 5-DOF upper-limb exoskeleton for power-assisted activity. The proposed 3-DOF upper-limb exoskeleton contains a 2-DOF shoulder joint and a 1-DOF internally rotated elbow joint. The structural parameters of the 3-DOF upper-limb exoskeleton were determined, and the differences and singularities of the two exoskeletons were analyzed. The workspace, the joint torques and the power consumption of two exoskeletons were analyzed by kinematics and dynamics, and an exoskeleton prototype experiment was performed. The results showed that, compared with a typical anthropomorphic upper-limb exoskeleton, the non-anthropomorphic 3-DOF upper-limb exoskeleton had the same actual workspace; eliminated singularities within the workspace; improved the elbow joint force situation; and the maximum elbow joint torque, elbow external-flexion/internal-extension and shoulder flexion/extension power consumption were significantly reduced. The proposed non-anthropomorphic 3-DOF upper-limb exoskeleton can be applied to a power-assisted upper-limb exoskeleton in industrial settings.

  8. A New Approach for Studying Nonlinear Dynamic Response of a Thin Plate with Internal Resonance in a Fractional Viscoelastic Medium

    Directory of Open Access Journals (Sweden)

    Yury A. Rossikhin

    2015-01-01

    Full Text Available In the previous analysis, the dynamic behaviour of a nonlinear plate embedded into a fractional derivative viscoelastic medium has been studied by the method of multiple time scales under the conditions of the internal resonances two-to-one and one-to-one, as well as the internal combinational resonances for the case when the linear parts of nonlinear equations of motion occur to be coupled. A new approach proposed in this paper allows one to uncouple the linear parts of equations of motion of the plate, while the same method, the method of multiple time scales, has been utilized for solving nonlinear equations. The influence of viscosity on the energy exchange mechanism between interacting nonlinear modes has been analyzed. It has been shown that for some internal resonances there exist such particular cases when it is possible to obtain two first integrals, namely, the energy integral and the stream function, which allows one to reduce the problem to the calculation of elliptic integrals. The new approach enables one to solve the problems of vibrations of thin bodies more efficiently.

  9. Nonlinear dynamics; Proceedings of the International Conference, New York, NY, December 17-21, 1979

    Science.gov (United States)

    Helleman, R. H. G.

    1980-01-01

    Papers were presented on turbulence, ergodic and integrable behavior, chaotic maps and flows, chemical and fully developed turbulence, and strange attractors. Specific attention was given to measures describing a turbulent flow, stochastization and collapse of vortex systems, a subharmonic route to turbulent convection, and weakly nonlinear turbulence in a rotating convection layer. The Korteweg-de Vries and Hill equations, plasma transport in three dimensions, a horseshoe in the dynamics of a forced beam, and the explosion of strange attractors exhibited by Duffing's equation were also considered.

  10. Sixth International Symposium on Bifurcations and Instabilities in Fluid Dynamics (BIFD2015)

    DEFF Research Database (Denmark)

    Bar-Yoseph, P. Z.; Brøns, Morten; Gelfgat, A.

    2016-01-01

    dynamics and remain a challenge for experimental, theoretical and computational studies. Examples of prototypical hydrodynamic instabilities are the Rayleigh–Bénard, Taylor–Couette, Bénard–Marangoni, Rayleigh–Taylor, and Kelvin–Helmholtz instabilities. A fundamental understanding of bifurcation patterns...... diseases, such as atherosclerotic and vulnerable plaques, abdominal aortic aneurisms, carotid artery disease, and pulmonary embolisms and implications for vascular interventions such as grafting and stenting. The collection of papers in this issue is a selection of the presentations given at the Sixth...

  11. Dynamic International Competitiveness of Transition Economies. What do trade figures tell us? The case of Poland

    DEFF Research Database (Denmark)

    Nielsen, Jørgen Ulff-Møller

    This paper shows that the reform on the structures of the Polish economy has had an impressively fast effect on the numbers of different products this country exports to Western countries. The time path may well be described by a logistic curve. The change in the exports of this country may...... therefore be characterised by a widening, instead of a deepening in specialisation. The paper introduces a new empirical methodology to evaluate the dynamic changes in export activities of a country. The result of this new methodology is that quality competition is becoming increasingly important for Poland...

  12. The dynamics in the international commercial changes in globalization terms-Comparison situation

    Directory of Open Access Journals (Sweden)

    Ph. D. Ion Gr. Ionescu

    2010-05-01

    Full Text Available The bigest weight of commercial changing of the country analysis have the manufactured products like: automobiles and industrial utilities, informatic products, ways of transportation,chimical products, thextile and footwear, this have 80% from total exports and 76% from total import. This fact is the consequence of recession of the working divizion , of speciality in industrial product, on branch and sub branch, on the type of products and subansanble of an morale abrasion for the product majority.The products of base have a low ponder in the exports and imports of this countries, they present a commercial balance and pasive for the raw metals and fuel, as the export of alimentary products, this country plais a role very important.So if it’s affected by the period of crisis, the international trade it has an important role in the sustain of economic growth of them. The sustain of this project are convinced that the introduction of the new coin will have positive feedback for the worldwide economy, confronted now with one of the most sedate crisis. And the european economy it will have, only to win from the project and the investitors can drop the unsure marketing from other continents for the investment in a stable region. With all of this the growth ot the european economy can be late, however, makes it doubt the succes of the „euro” project. The International Monetary Fond have seen that the eleven european countries that adopted euro at the 1st of January 2006, a growth of the Intern Brute Porduct (IBP of 2,4% (same as for European Union, 2,6% in spring with 0,4% less then 2005, the growth that classifies as „solid and continuous”.

  13. The extensive international use of commercial computational fluid dynamics (CFD) codes

    International Nuclear Information System (INIS)

    Hartmut Wider

    2005-01-01

    What are the main reasons for the extensive international success of commercial CFD codes? This is due to their ability to calculate the fine structures of the investigated processes due to their versatility, their numerical stability and that they can guarantee the proper solution in most cases. This was made possible by the constantly increasing computer power at an ever more affordable prize. Furthermore it is much more efficient to have researchers use a CFD code rather than to develop a similar code system due to the time consuming nature of this activity and the high probability of hidden coding errors. The centralized development and upgrading makes these reliable CFD codes possible and affordable. However, the CFD companies' developments are naturally concentrated on the most profitable areas, and thus, if one works in a 'non-priority' field one cannot use them. Moreover, the prize of renting CFD codes, applications to complex systems such as whole nuclear reactors and the need to teach students gives the development of self-made codes still plenty of room. But CFD codes can model detailed aspects of large systems and subroutines generated by users can be added. Since there are only a few heavily used CFD codes such as FLUENT, STAR-CD, ANSYS CFX, these are used in many countries. Also international training courses are given and the news bulletins of these codes help to spread the news on further developments. A larger number of international codes would increase the competition but would at the same time make it harder to select the most appropriate CFD code for a given problem. Examples will be presented of uses of CFD codes as more detailed system codes for the decay heat removal from reactors, the application to aerosol physics and the application to heavy metal fluids using different turbulence models. (author)

  14. 3rd International Conference on Dynamics, Games and Science & 7th Berkeley Bioeconomy Conference

    CERN Document Server

    Zilberman, David

    2017-01-01

    The concepts and techniques presented in this volume originated from the fields of dynamics, statistics, control theory, computer science and informatics, and are applied to novel and innovative real-world applications. Over the past few decades, the use of dynamic systems, control theory, computing, data mining, machine learning and simulation has gained the attention of numerous researchers from all over the world. Admirable scientific projects using both model-free and model-based methods coevolved at today’s research centers and are introduced in conferences around the world, yielding new scientific advances and helping to solve important real-world problems. One important area of progress is the bioeconomy, where advances in the life sciences are used to produce new products in a sustainable and clean manner. In this book, scientists from all over the world share their latest insights and important findings in the field.  The majority of the contributed papers for this volume were written by particip...

  15. Kink dynamics in a parametric ϕ 6 system: a model with controllably many internal modes

    Science.gov (United States)

    Demirkaya, A.; Decker, R.; Kevrekidis, P. G.; Christov, I. C.; Saxena, A.

    2017-12-01

    We explore a variant of the ϕ 6 model originally proposed in Phys. Rev. D 12 (1975) 1606 as a prototypical, so-called, "bag" model in which domain walls play the role of quarks within hadrons. We examine the steady state of the model, namely an apparent bound state of two kink structures. We explore its linearization, and we find that, as a function of a parameter controlling the curvature of the potential, an effectively arbitrary number of internal modes may arise in the point spectrum of the linearization about the domain wall profile. We explore some of the key characteristics of kink-antikink collisions, such as the critical velocity and the multi-bounce windows, and how they depend on the principal parameter of the model. We find that the critical velocity exhibits a non-monotonic dependence on the parameter controlling the curvature of the potential. For the multi-bounce windows, we find that their range and complexity decrease as the relevant parameter decreases (and as the number of internal modes in the model increases). We use a modified collective coordinates method [in the spirit of recent works such as Phys. Rev. D 94 (2016) 085008] in order to capture the relevant phenomenology in a semi-analytical manner.

  16. The Dynamics of Daylighting at a Residential College Building with the Internal Courtyard Arrangement

    Directory of Open Access Journals (Sweden)

    Adi Ainurzaman Jamaludin

    2015-11-01

    Full Text Available Dayasari residential college building was designed with the internal courtyard that allows for numerous implementations of bioclimatic design strategies, especially on daylighting. The field measurement was conducted at eight unoccupied student rooms, selected as samples to represent ten scenarios and orientations that concerned with the level of radiation and penetration of sunlight. This study reveals the contribution of the internal courtyard in the residential college which allows the daylight penetration at the corridor areas and interior of the rooms through the transom over the entrance door, up to ten hours daily. Different amounts of daylight were measured in specific room scenarios to suggest on the most comfortable indoor living space. The recorded mean value for indoor varied from 37 to 286 lux, while in the corridor area 192 to 3,848 lux. However, the use of the large overhangs over the windows, wall openings in the room and trees with large canopy in the landscape setting should critically justify when the adequacy of daylight was drastically reduced in certain rooms.

  17. Dynamics of the international coffee market and instrumental in price formation

    Directory of Open Access Journals (Sweden)

    Ricardo Candéa Sá Barreto

    2016-12-01

    Full Text Available This study's main general objective of studying the behavior of coffee beans on the international market. Empirical analysis uses econometric tool as a model of simultaneous equations using least squares in a three-stage annual data base extending over the period 1964 / 65-2014 / 15. The results suggest that the factors that affect the production of coffee beans are the actual prices and the planted area. However, demand is affected by the growth of the world economy. The price simulations for the period 2014/15 - 2020/21 indicate that a yearly growth (GDP of 2.1% there is a tendency of small high price to 3.6% moderate rise in the price of coffee until 2018/19 and a stronger growth trend of prices from 2019/20 and a growth of 4.7% a high coffee prices trend in grain on the international market. Thus the tendency of the projections 3 and the key market factors continue to favor the maintenance of current high coffee prices. For the full period 1964/65 to 2014/15 there is a moderate relationship between coffee prices and the stock. It follows that the results obtained with the scenarios developed in this work can be useful to rethink measures to recover income from coffee producing countries

  18. MO-F-CAMPUS-J-03: Sorting 2D Dynamic MR Images Using Internal Respiratory Signal for 4D MRI

    International Nuclear Information System (INIS)

    Wen, Z; Hui, C; Beddar, S; Stemkens, B; Tijssen, R; Berg, C van den

    2015-01-01

    Purpose: To develop a novel algorithm to extract internal respiratory signal (IRS) for sorting dynamic magnetic resonance (MR) images in order to achieve four-dimensional (4D) MR imaging. Methods: Dynamic MR images were obtained with the balanced steady state free precession by acquiring each two-dimensional sagittal slice repeatedly for more than one breathing cycle. To generate a robust IRS, we used 5 different representative internal respiratory surrogates in both the image space (body area) and the Fourier space (the first two low-frequency phase components in the anterior-posterior direction, and the first two low-frequency phase components in the superior-inferior direction). A clustering algorithm was then used to search for a group of similar individual internal signals, which was then used to formulate the final IRS. A phantom study and a volunteer study were performed to demonstrate the effectiveness of this algorithm. The IRS was compared to the signal from the respiratory bellows. Results: The IRS computed by our algorithm matched well with the bellows signal in both the phantom and the volunteer studies. On average, the normalized cross correlation between the IRS and the bellows signal was 0.97 in the phantom study and 0.87 in the volunteer study, respectively. The average difference between the end inspiration times in the IRS and bellows signal was 0.18 s in the phantom study and 0.14 s in the volunteer study, respectively. 4D images sorted based on the IRS showed minimal mismatched artifacts, and the motion of the anatomy was coherent with the respiratory phases. Conclusion: A novel algorithm was developed to generate IRS from dynamic MR images to achieve 4D MR imaging. The performance of the IRS was comparable to that of the bellows signal. It can be easily implemented into the clinic and potentially could replace the use of external respiratory surrogates. This research was partially funded by the the Center for Radiation Oncology Research from

  19. Dynamic Establishment of Weight of Enterprise’s Internal Function Based on AHP and QFD

    Directory of Open Access Journals (Sweden)

    He Pei

    2017-01-01

    Full Text Available Modern enterprise management strives to become effective and pragmatic, usually, KPI is the most essential key indicator for the enterprise examination department. However, because the supporting and bearing roles of KPI for different departments are different, no a rather scientific quantification for the weight between them is available, unbalanced examination weights between indicators and departments usually exists. Here, it is with balanced score card to breakdown enterprise’s key tasks, card the performance indicators supporting enterprise’s key tasks, and utilize AHP and QFD method to dynamically establish a standard for measuring each department’s indicators so as to provide a basis for enterprise’s scientific examination.

  20. Analysis of heat release dynamics in an internal combustion engine using multifractals and wavelets

    International Nuclear Information System (INIS)

    Sen, A.K.; Litak, G.; Finney, C.E.A.; Daw, C.S.; Wagner, R.M.

    2010-01-01

    In this paper we analyze data from previously reported experimental measurements of cycle-to-cycle combustion variations in a lean-fueled, multi-cylinder spark-ignition (SI) engine. We characterize the changes in the observed combustion dynamics with as-fed fuel-air ratio using conventional histograms and statistical moments, and we further characterize the shifts in combustion complexity in terms of multifractals and wavelet decomposition. Changes in the conventional statistics and multifractal structure indicate trends with fuel-air ratio that parallel earlier reported observations. Wavelet decompositions reveal persistent, non-stochastic oscillation modes at higher fuel-air ratios that were not obvious in previous analyses. Recognition of these long-time-scale, non-stochastic oscillations is expected to be useful for improving modelling and control of engine combustion variations and multi-cylinder balancing.

  1. Proceedings of the 20th International Symposium on Space Flight Dynamics

    Science.gov (United States)

    Woodard, Mark (Editor); Stengle, Tom (Editor)

    2007-01-01

    Topics include: Measuring Image Navigation and Registration Performance at the 3-Sigma Level Using Platinum Quality Landmarks; Flight Dynamics Performances of the MetOp A Satellite during the First Months of Operations; Visual Navigation - SARE Mission; Determining a Method of Enabling and Disabling the Integral Torque in the SDO Science and Inertial Mode Controllers; Guaranteeing Pointing Performance of the SDO Sun-Pointing Controllers in Light of Nonlinear Effects; SDO Delta H Mode Design and Analysis; Observing Mode Attitude Controller for the Lunar Reconnaissance Orbiter; Broken-Plane Maneuver Applications for Earth to Mars Trajectories; ExoMars Mission Analysis and Design - Launch, Cruise and Arrival Analyses; Mars Reconnaissance Orbiter Aerobraking Daily Operations and Collision Avoidance; Mars Reconnaissance Orbiter Interplanetary Cruise Navigation; Motion Parameters Determination of the SC and Phobos in the Project Phobos-Grunt; GRAS NRT Precise Orbit Determination: Operational Experience; Orbit Determination of LEO Satellites for a Single Pass through a Radar: Comparison of Methods; Orbit Determination System for Low Earth Orbit Satellites; Precise Orbit Determination for ALOS; Anti-Collision Function Design and Performances of the CNES Formation Flying Experiment on the PRISMA Mission; CNES Approaching Guidance Experiment within FFIORD; Maneuver Recovery Analysis for the Magnetospheric Multiscale Mission; SIMBOL-X: A Formation Flying Mission on HEO for Exploring the Universe; Spaceborne Autonomous and Ground Based Relative Orbit Control for the TerraSAR-X/TanDEM-X Formation; First In-Orbit Experience of TerraSAR-X Flight Dynamics Operations; Automated Target Planning for FUSE Using the SOVA Algorithm; Space Technology 5 Post-Launch Ground Attitude Estimation Experience; Standardizing Navigation Data: A Status Update; and A Study into the Method of Precise Orbit Determination of a HEO Orbiter by GPS and Accelerometer.

  2. Internal models of target motion: expected dynamics overrides measured kinematics in timing manual interceptions.

    Science.gov (United States)

    Zago, Myrka; Bosco, Gianfranco; Maffei, Vincenzo; Iosa, Marco; Ivanenko, Yuri P; Lacquaniti, Francesco

    2004-04-01

    Prevailing views on how we time the interception of a moving object assume that the visual inputs are informationally sufficient to estimate the time-to-contact from the object's kinematics. Here we present evidence in favor of a different view: the brain makes the best estimate about target motion based on measured kinematics and an a priori guess about the causes of motion. According to this theory, a predictive model is used to extrapolate time-to-contact from expected dynamics (kinetics). We projected a virtual target moving vertically downward on a wide screen with different randomized laws of motion. In the first series of experiments, subjects were asked to intercept this target by punching a real ball that fell hidden behind the screen and arrived in synchrony with the visual target. Subjects systematically timed their motor responses consistent with the assumption of gravity effects on an object's mass, even when the visual target did not accelerate. With training, the gravity model was not switched off but adapted to nonaccelerating targets by shifting the time of motor activation. In the second series of experiments, there was no real ball falling behind the screen. Instead the subjects were required to intercept the visual target by clicking a mousebutton. In this case, subjects timed their responses consistent with the assumption of uniform motion in the absence of forces, even when the target actually accelerated. Overall, the results are in accord with the theory that motor responses evoked by visual kinematics are modulated by a prior of the target dynamics. The prior appears surprisingly resistant to modifications based on performance errors.

  3. Inferring internal properties of Earth's core dynamics and their evolution from surface observations and a numerical geodynamo model

    Directory of Open Access Journals (Sweden)

    J. Aubert

    2011-10-01

    Full Text Available Over the past decades, direct three-dimensional numerical modelling has been successfully used to reproduce the main features of the geodynamo. Here we report on efforts to solve the associated inverse problem, aiming at inferring the underlying properties of the system from the sole knowledge of surface observations and the first principle dynamical equations describing the convective dynamo. To this end we rely on twin experiments. A reference model time sequence is first produced and used to generate synthetic data, restricted here to the large-scale component of the magnetic field and its rate of change at the outer boundary. Starting from a different initial condition, a second sequence is next run and attempts are made to recover the internal magnetic, velocity and buoyancy anomaly fields from the sparse surficial data. In order to reduce the vast underdetermination of this problem, we use stochastic inversion, a linear estimation method determining the most likely internal state compatible with the observations and some prior knowledge, and we also implement a sequential evolution algorithm in order to invert time-dependent surface observations. The prior is the multivariate statistics of the numerical model, which are directly computed from a large number of snapshots stored during a preliminary direct run. The statistics display strong correlation between different harmonic degrees of the surface observations and internal fields, provided they share the same harmonic order, a natural consequence of the linear coupling of the governing dynamical equations and of the leading influence of the Coriolis force. Synthetic experiments performed with a weakly nonlinear model yield an excellent quantitative retrieval of the internal structure. In contrast, the use of a strongly nonlinear (and more realistic model results in less accurate static estimations, which in turn fail to constrain the unobserved small scales in the time integration of the

  4. Dynamics of Professional and Communicative Tolerance in Educating International Relations Specialists

    Directory of Open Access Journals (Sweden)

    Alexander L. Temnitskiy

    2014-01-01

    Full Text Available Under the conditions of the accelerated development of Russian economics, commercial sector and due to a great number of international private companies we can see the intensified problem of tolerance of future diplomats, international specialists, regarding to the system, its the main components such as political, economic, military. It is supposed, that in the modern student environment of future diplomats we can notice the exaltation of values of individual pragmatism and increasing the lack of sociality by deciding of questions about their present and future professional activity. Sociological researches carried out among the students of faculty of international affairs in 2002, 2007 and 2012 review different factors of professional and communicative tolerance. The author of this article markes and diagnoses the materially - pragmatic and art-substantial values of the chosen profession and it's given an interpretation of value orientations content on the categories of employment after the university graduation. Students' estimations define the personal competents of government employee, which are necessary for the successful carrier in the system of MFA of Russia. The interpretation and the real content of communicative tolerance levels are reviewed in the article. The ethnic component of communicative tolerance is studied separately. In conclusion of the article we can define the role of material differentiation of students in the context of communicative tolerance. According to the analyse it is confuted the initial supposition about the glorification of individual pragmatic values and shortage of social responsibility in the student environment. It was found out, that in the communicative tolerance the level of empathy in the personal contact is keeping to be prevalent and stable according to different years of survey. However, it is deduced, the occurred for 10 years the growth of students material welfare didn't contribute to the growth

  5. Dynamic estimator for determining operating conditions in an internal combustion engine

    Science.gov (United States)

    Hellstrom, Erik; Stefanopoulou, Anna; Jiang, Li; Larimore, Jacob

    2016-01-05

    Methods and systems are provided for estimating engine performance information for a combustion cycle of an internal combustion engine. Estimated performance information for a previous combustion cycle is retrieved from memory. The estimated performance information includes an estimated value of at least one engine performance variable. Actuator settings applied to engine actuators are also received. The performance information for the current combustion cycle is then estimated based, at least in part, on the estimated performance information for the previous combustion cycle and the actuator settings applied during the previous combustion cycle. The estimated performance information for the current combustion cycle is then stored to the memory to be used in estimating performance information for a subsequent combustion cycle.

  6. Nonlinear dynamics of mini-satellite respinup by weak internal controllable torques

    Energy Technology Data Exchange (ETDEWEB)

    Somov, Yevgeny, E-mail: e-somov@mail.ru [Samara State Technical University, Department for Guidance, Navigation and Control, 244 Molodogvardeyskaya Str., Samara 443100 (Russian Federation)

    2014-12-10

    Contemporary space engineering advanced new problem before theoretical mechanics and motion control theory: a spacecraft directed respinup by the weak restricted control internal forces. The paper presents some results on this problem, which is very actual for energy supply of information mini-satellites (for communication, geodesy, radio- and opto-electronic observation of the Earth et al.) with electro-reaction plasma thrusters and gyro moment cluster based on the reaction wheels or the control moment gyros. The solution achieved is based on the methods for synthesis of nonlinear robust control and on rigorous analytical proof for the required spacecraft rotation stability by Lyapunov function method. These results were verified by a computer simulation of strongly nonlinear oscillatory processes at respinuping of a flexible spacecraft.

  7. International evidence on crude oil price dynamics. Applications of ARIMA-GARCH models

    International Nuclear Information System (INIS)

    Mohammadi, Hassan; Su, Lixian

    2010-01-01

    We examine the usefulness of several ARIMA-GARCH models for modeling and forecasting the conditional mean and volatility of weekly crude oil spot prices in eleven international markets over the 1/2/1997-10/3/2009 period. In particular, we investigate the out-of-sample forecasting performance of four volatility models - GARCH, EGARCH and APARCH and FIGARCH over January 2009 to October 2009. Forecasting results are somewhat mixed, but in most cases, the APARCH model outperforms the others. Also, conditional standard deviation captures the volatility in oil returns better than the traditional conditional variance. Finally, shocks to conditional volatility dissipate at an exponential rate, which is consistent with the covariance-stationary GARCH models than the slow hyperbolic rate implied by the FIGARCH alternative. (author)

  8. Nonlinear dynamics of mini-satellite respinup by weak internal controllable torques

    Science.gov (United States)

    Somov, Yevgeny

    2014-12-01

    Contemporary space engineering advanced new problem before theoretical mechanics and motion control theory: a spacecraft directed respinup by the weak restricted control internal forces. The paper presents some results on this problem, which is very actual for energy supply of information mini-satellites (for communication, geodesy, radio- and opto-electronic observation of the Earth et al.) with electro-reaction plasma thrusters and gyro moment cluster based on the reaction wheels or the control moment gyros. The solution achieved is based on the methods for synthesis of nonlinear robust control and on rigorous analytical proof for the required spacecraft rotation stability by Lyapunov function method. These results were verified by a computer simulation of strongly nonlinear oscillatory processes at respinuping of a flexible spacecraft.

  9. Fluid dynamic modeling of junctions in internal combustion engine inlet and exhaust systems

    Science.gov (United States)

    Chalet, David; Chesse, Pascal

    2010-10-01

    The modeling of inlet and exhaust systems of internal combustion engine is very important in order to evaluate the engine performance. This paper presents new pressure losses models which can be included in a one dimensional engine simulation code. In a first part, a CFD analysis is made in order to show the importance of the density in the modeling approach. Then, the CFD code is used, as a numerical test bench, for the pressure losses models development. These coefficients depend on the geometrical characteristics of the junction and an experimental validation is made with the use of a shock tube test bench. All the models are then included in the engine simulation code of the laboratory. The numerical calculation of unsteady compressible flow, in each pipe of the inlet and exhaust systems, is made and the calculated engine torque is compared with experimental measurements.

  10. Beyond the internal dynamics of organizational responses to conflicting institutional demands

    Directory of Open Access Journals (Sweden)

    Viviana Gutiérrez‐Rincón

    2014-10-01

    Full Text Available This paper presents some reflections on strategic response models, in particular the models proposed by Pache, Santos and Oliver, and it evaluates their complementarity and differences, especially regarding the interactions between decision making and the possible strategic responses to institutional demands. It is argued that the theoretical contributions of Pache and Santos can be categorized under the dimension of utility, because they can enhance the potential to operationalize and test the model. However, the reflections made in this paper not only highlight the need to take into account other external and internal factors for the study of strategic responses, but also the integration of different linkages of the decision process with strategic responses to institutional demands.

  11. The broadband microwave spectra of the monoterpenoids thymol and carvacrol: Conformational landscape and internal dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Schmitz, D.; Shubert, V. A. [Max Planck Institute for the Structure and Dynamics of Matter, Hamburg (Germany); The Center for Free-Electron Laser Science, Hamburg (Germany); Giuliano, B. M. [Center for Astrobiology, INTA-CSIC, Torrejón de Ardoz, Madrid (Spain); Schnell, M., E-mail: melanie.schnell@mpsd.mpg.de [Max Planck Institute for the Structure and Dynamics of Matter, Hamburg (Germany); The Center for Free-Electron Laser Science, Hamburg (Germany); The Hamburg Centre for Ultrafast Imaging, Universität Hamburg, Hamburg (Germany)

    2014-07-21

    The rotational spectra of the monoterpenoids thymol and carvacrol are reported in the frequency range 2–8.5 GHz, obtained with broadband Fourier-transform microwave spectroscopy. For carvacrol four different conformations were identified in the cold conditions of the molecular jet, whereas only three conformations were observed for thymol. The rotational constants and other molecular parameters are reported and compared with quantum chemical calculations. For both molecules, line splittings due to methyl group internal rotation were observed and the resulting barrier heights could be determined. The experimental barrier heights, 4.0863(25) kJ/mol for trans-carvacrol-A, 4.4024(16) kJ/mol for trans-carvacrol-B, and 0.3699(11) kJ/mol for trans-thymol-A, are compared with similar molecules.

  12. The broadband microwave spectra of the monoterpenoids thymol and carvacrol: Conformational landscape and internal dynamics

    International Nuclear Information System (INIS)

    Schmitz, D.; Shubert, V. A.; Giuliano, B. M.; Schnell, M.

    2014-01-01

    The rotational spectra of the monoterpenoids thymol and carvacrol are reported in the frequency range 2–8.5 GHz, obtained with broadband Fourier-transform microwave spectroscopy. For carvacrol four different conformations were identified in the cold conditions of the molecular jet, whereas only three conformations were observed for thymol. The rotational constants and other molecular parameters are reported and compared with quantum chemical calculations. For both molecules, line splittings due to methyl group internal rotation were observed and the resulting barrier heights could be determined. The experimental barrier heights, 4.0863(25) kJ/mol for trans-carvacrol-A, 4.4024(16) kJ/mol for trans-carvacrol-B, and 0.3699(11) kJ/mol for trans-thymol-A, are compared with similar molecules

  13. Enantio- and Stereoselective Construction of Atisane Scaffold via Organocatalytic Intramolecular Michael Reaction and Diels-Alder Reaction.

    Science.gov (United States)

    Sekita, Hiroko; Adachi, Kyohei; Kobayashi, Ippei; Sato, Yusuke; Nakada, Masahisa

    2017-05-05

    An enantio- and stereoselective construction of the atisane scaffold via organocatalytic intramolecular Michael reaction and Diels-Alder reaction is described. The organocatalytic intramolecular Michael reaction has been found to stereoselectively generate a trans-stereodiad comprising an all-carbon quaternary and a tertiary stereogenic centers. Use of the chiral secondary amine bearing thiourea with benzoic acid as additive is the key to obtaining the desired product with excellent ee in synthetically acceptable yield. The prepared chiral building block has been successfully converted to the compound including the atisane scaffold via the highly stereoselective intramolecular Diels-Alder reaction.

  14. Proceedings of the 2nd international advisory committee on biomolecular dynamics instrument DNA in MLF at J-PARC

    International Nuclear Information System (INIS)

    Arai, Masatoshi; Aizawa, Kazuya; Nakajima, Kenji; Shibata, Kaoru; Takahashi, Nobuaki

    2009-07-01

    The 2nd International Advisory Committee on the 'Biomolecular Dynamics Backscattering Spectrometer DNA' was held on November 12th - 13th, 2008 at J-PARC Center, Japan Atomic Energy Agency. This IAC has been organized for aiming to realize an innovative neutron backscattering instrument in the Materials and Life Science Experimental Facility (MLF) at the J-PARC and therefore four leading scientists in the field of neutron backscattering instruments has been selected as the member (Dr. Dan Neumann (Chair); Prof. Ferenc Mezei; Dr. Hannu Mutka; Dr. Philip Tregenna-Piggott), and the 1st IAC had been held on February 27th - 29th, 2008. This report includes the executive summary and materials of the presentations in the 2nd IAC. (author)

  15. Poloidal rotation dynamics, radial electric field, and neoclassical theory in the jet internal-transport-barrier region.

    Science.gov (United States)

    Crombé, K; Andrew, Y; Brix, M; Giroud, C; Hacquin, S; Hawkes, N C; Murari, A; Nave, M F F; Ongena, J; Parail, V; Van Oost, G; Voitsekhovitch, I; Zastrow, K-D

    2005-10-07

    Results from the first measurements of a core plasma poloidal rotation velocity (upsilontheta) across internal transport barriers (ITB) on JET are presented. The spatial and temporal evolution of the ITB can be followed along with the upsilontheta radial profiles, providing a very clear link between the location of the steepest region of the ion temperature gradient and localized spin-up of upsilontheta. The upsilontheta measurements are an order of magnitude higher than the neoclassical predictions for thermal particles in the ITB region, contrary to the close agreement found between the determined and predicted particle and heat transport coefficients [K.-D. Zastrow, Plasma Phys. Controlled Fusion 46, B255 (2004)]. These results have significant implications for the understanding of transport barrier dynamics due to their large impact on the measured radial electric field profile.

  16. Asymmetric learning by doing and dynamically efficient policy: implications for domestic and international emissions permit trading of allocating permits usefully

    International Nuclear Information System (INIS)

    Read, Peter

    2000-01-01

    Learning by doing leads to cost reductions as suppliers move down the 'experience curve'. This results in a beneficial supply side inter-temporal externality that, for dynamic efficiency, requires a higher incentive for abatement innovations than the penalty on emissions. This effect can be achieved by a dedicated emissions tax or by a proportionate abatement obligation or by allocating permits usefully. The latter arrangement is compatible with the effective cap on emissions that is secured by an emissions trading scheme. Each of the three possibilities results in a reduced loss of international competitivity in policy-committed regions, in less 'leakage, and in more technology transfer. Implications for trading in emissions permits and in project-related credits are discussed. (Author)

  17. The dynamics of fauna and population of birds in agricultural landscapes on the border of Kazan International Airport

    Science.gov (United States)

    Bespalov, A. F.; Belyaev, A. N.

    2018-01-01

    The dynamics of fauna and population of birds from agricultural lands near Kazan International Airport has been studied for one year. A total of 60 bird species have been registered, of which 26 species must be considered as highly dangerous to flying aircraft. With regard to seasonal activity, the nesting period (April - June) is the most hazardous, since it is characterized by maximum species richness and total population density of birds, as well as their high species diversity. Furthermore, a serious danger is posed by the period of postnesting nomadic movements and the onset of migrations (July - September) when the species diversity turns out to be the highest and the total population density begins to decrease. It has been recommended based on the obtained results that the current crops should be replaced by cultivars that will be less attractive to birds. In spring and autumn, certain bird hazing and frightening measures must be taken on a more regular basis.

  18. 2nd International Symposium "Atomic Cluster Collisions : Structure and Dynamics from the Nuclear to the Biological Scale"

    CERN Document Server

    Solov'yov, Andrey; ISACC 2007; Latest advances in atomic cluster collisions

    2008-01-01

    This book presents a 'snapshot' of the most recent and significant advances in the field of cluster physics. It is a comprehensive review based on contributions by the participants of the 2nd International Symposium on Atomic Cluster Collisions (ISACC 2007) held in July 19-23, 2007 at GSI, Darmstadt, Germany. The purpose of the Symposium is to promote the growth and exchange of scientific information on the structure and properties of nuclear, atomic, molecular, biological and complex cluster systems studied by means of photonic, electronic, heavy particle and atomic collisions. Particular attention is devoted to dynamic phenomena, many-body effects taking place in cluster systems of a different nature - these include problems of fusion and fission, fragmentation, collective electron excitations, phase transitions, etc.Both the experimental and theoretical aspects of cluster physics, uniquely placed between nuclear physics on the one hand and atomic, molecular and solid state physics on the other, are discuss...

  19. Dynamic effects on the acceptance of hydrogen technologies - an international comparison

    International Nuclear Information System (INIS)

    Heinz, Boris; Erdmann, Georg

    2008-01-01

    Social acceptance plays an important role for the future hydrogen economy and a broad market launch of hydrogen technologies. Neglecting the aspect of public acceptance and attitude may become a serious obstacle for the establishment of a mass market infrastructure. With a standardized questionnaire and a standardized procedure, personal interviews were conducted with at least 300 persons in Amsterdam, Barcelona, Berlin, Hamburg, London, Luxembourg, Madrid and Reykjavik, in total with 3352 persons. Thus the dynamics of the public attitude toward hydrogen were analyzed, whereby the possibility of setbacks and accidents was taken into consideration. Whereas 68% of the interviewed persons would be supportive of the aforementioned technologies, an amount of 31% was determined to be volatile. An amount of 77% stated that they would use a hydrogen bus instead of a conventional one if they could choose, but an amount of 21% was indifferent. It will be shown how these amounts can affect the balance of acceptance and how stable the acceptance of hydrogen technologies can be considered in the evaluated six countries. (author)

  20. Internal representation of task rules by recurrent dynamics: the importance of the diversity of neural responses

    Directory of Open Access Journals (Sweden)

    Mattia Rigotti

    2010-10-01

    Full Text Available Neural activity of behaving animals, especially in the prefrontal cortex, is highly heterogeneous, with selective responses to diverse aspects of the executed task. We propose a general model of recurrent neural networks that perform complex rule-based tasks, and we show that the diversity of neuronal responses plays a fundamental role when the behavioral responses are context dependent. Specifically, we found that when the inner mental states encoding the task rules are represented by stable patterns of neural activity (attractors of the neural dynamics, the neurons must be selective for combinations of sensory stimuli and inner mental states. Such mixed selectivity is easily obtained by neurons that connect with random synaptic strengths both to the recurrent network and to neurons encoding sensory inputs. The number of randomly connected neurons needed to solve a task is on average only three times as large as the number of neurons needed in a network designed ad hoc. Moreover, the number of needed neurons grows only linearly with the number of task-relevant events and mental states, provided that each neuron responds to a large proportion of events (dense/distributed coding. A biologically realistic implementation of the model captures several aspects of the activity recorded from monkeys performing context dependent tasks. Our findings explain the importance of the diversity of neural responses and provide us with simple and general principles for designing attractor neural networks that perform complex computation.

  1. Reorganization of personal identity in the context of motivational dynamics and internal dialogical activity.

    Science.gov (United States)

    Batory, Anna

    2014-08-01

    Identity is constantly constructed and reconstructed. It may be assumed that there are six fundamental motivational goals according to which it is organized: self-esteem, self-efficacy, continuity, distinctiveness, belonging, and meaning (Vignoles, 2011). Moreover, identity is shaped by its dialogical nature (Hermans, 2003; van Halen & Janssen, 2004). The longitudinal study was conducted to examine both the motivational and the dialogical basis of identity structure dynamics. The results showed that the more the identity element was connected with a sense of continuity and the more dialogical it was, the greater the perceived centrality of this element was after two months. Furthermore, the more the identity element satisfied the self-esteem and belonging motives, the more positive was the affect ascribed to it. In the behavioral domain of identity, participants more strongly manifested those identity aspects that were earlier rated as more dialogical and satisfying the motive of belonging. The results showed that the motivational underpinnings of identity along with its dialogical nature explain changes in identity structure. © 2014 Scandinavian Psychological Associations and John Wiley & Sons Ltd.

  2. A study of internal energy relaxation in shocks using molecular dynamics based models

    International Nuclear Information System (INIS)

    Li, Zheng; Parsons, Neal; Levin, Deborah A.

    2015-01-01

    Recent potential energy surfaces (PESs) for the N 2 + N and N 2 + N 2 systems are used in molecular dynamics (MD) to simulate rates of vibrational and rotational relaxations for conditions that occur in hypersonic flows. For both chemical systems, it is found that the rotational relaxation number increases with the translational temperature and decreases as the rotational temperature approaches the translational temperature. The vibrational relaxation number is observed to decrease with translational temperature and approaches the rotational relaxation number in the high temperature region. The rotational and vibrational relaxation numbers are generally larger in the N 2 + N 2 system. MD-quasi-classical trajectory (QCT) with the PESs is also used to calculate the V-T transition cross sections, the collision cross section, and the dissociation cross section for each collision pair. Direct simulation Monte Carlo (DSMC) results for hypersonic flow over a blunt body with the total collision cross section from MD/QCT simulations, Larsen-Borgnakke with new relaxation numbers, and the N 2 dissociation rate from MD/QCT show a profile with a decreased translational temperature and a rotational temperature close to vibrational temperature. The results demonstrate that many of the physical models employed in DSMC should be revised as fundamental potential energy surfaces suitable for high temperature conditions become available

  3. Internal stress evolution in Fe laths deformed at low temperature analysed by dislocation dynamics simulations

    International Nuclear Information System (INIS)

    Chaussidon, Julien; Fivel, Marc; Robertson, Christian; Marini, Bernard

    2010-01-01

    Stress evolution in Fe laths undergoing plastic deformation is investigated using three-dimensional dislocation dynamics simulations adapted to body centred cubic crystals, in the ductile to brittle transition temperature range. The selected boundary conditions, applied stress tensor and initial dislocation structures account for the realistic microstructure observed in bainitic steels. The effective stress field projected in the three different {1 0 0}cleavage planes is calculated for two different temperatures (50 and 200 K) and presented quantitatively, in the form of stress/frequency diagrams. It is shown that plastic activity tends to relax the stress acting in certain cleavage planes (the (0 1 0) and (0 0 1) planes) while, at the same time, amplifying the stress acting in other cleavage planes (the (1 0 0) planes). The selective stress amplification in the latter planes depends on the applied load direction, in combination with the limited set of available slip systems and the lath geometry. In the examined configuration, this selection effect is more pronounced with decreasing temperature, emphasizing the role of thermally activated plasticity on deformation-induced stress concentrations

  4. Self adaptive internal combustion engine control for hydrogen mixtures using piezoelectric transducers for dynamic cylinder pressure monitoring

    Energy Technology Data Exchange (ETDEWEB)

    Courteau, R.; Bose, T.K. [Quebec Univ., Trois-Rivieres, PQ (Canada). Institut de recherche sur l' hydrogene

    2004-07-01

    Hydrogen internal combustion engine research at the Hydrogen Research Institute includes the following infrastructure: a 20 square metre test cell, an engine preparation room, a 150 hp dynamometer, exhaust gas analysers and a hydrogen supply. The goal of the research is to develop internal combustion engine technologies that can use hydrogen as a fuel without knocking, backfires, excessive engine wear, and with low emissions. As well as hydrogen, fuels such as biogas are also investigated. Technologies under investigation include adaptive control algorithms, as well as advanced sensors and actuators. The latter include piezolelectrics, optical fibres, nitrogen oxide detectors, and chemical composition detectors. Developments include microprocessor-controlled injection and ignition control systems for both single cylinder and multicylinder engines. Research on the influence of fuel composition on best ignition timing is presented. There is also dynamic cylinder pressure monitoring to prevent knocking make engine state assessments and perform engine calibration. Piezoelectric cylinder pressure sensors are employed, either integrated with the spark plugs, or stand-alone, inserted through separate holes through the cylinder head. tabs, figs.

  5. Influence of different breathing maneuvers on internal and external organ motion: Use of fiducial markers in dynamic MRI

    International Nuclear Information System (INIS)

    Plathow, Christian; Zimmermann, Hendrik; Fink, Christian; Umathum, Reiner; Schoebinger, Max; Huber, Peter; Zuna, Ivan; Debus, Juergen; Schlegel, Wolfgang; Meinzer, Hans-Peter; Semmler, Wolfhard; Kauczor, Hans-Ulrich; Bock, Michael

    2005-01-01

    Purpose: To investigate, with dynamic magnetic resonance imaging (dMRI) and a fiducial marker, the influence of different breathing maneuvers on internal organ and external chest wall motion. Methods and materials: Lung and chest wall motion of 16 healthy subjects (13 male, 3 female) were examined with real-time trueFISP (true fast imaging with steady-state precession) dMRI and a small inductively coupled marker coil on either the abdomen or thorax. Three different breathing maneuvers were performed (predominantly 'abdominal breathing,' 'thoracic breathing,' and unspecific 'normal breathing'). The craniocaudal (CC), anteroposterior (AP), and mediolateral (ML) lung distances were correlated (linear regression coefficient) with marker coil position during forced and quiet breathing. Results: Differences of the CC distance between maximum forced inspiration and expiration were significant between abdominal and thoracic breathing (p < 0.05). The correlation between CC distance and coil position was best for forced abdominal breathing and a marker coil in the abdominal position (r 0.89 ± 0.04); for AP and ML distance, forced thoracic breathing and a coil in the thoracic position was best (r = 0.84 ± 0.03 and 0.82 ± 0.03, respectively). In quiet breathing, a lower correlation was found. Conclusion: A fiducial marker coil external to the thorax in combination with dMRI is a new technique to yield quantitative information on the correlation of internal organ and external chest wall motion. Correlations are highly dependent on the breathing maneuver

  6. Internal dynamics and emittance growth in space-charge-dominated beams

    International Nuclear Information System (INIS)

    Anderson, O.A.

    1987-01-01

    Previous analytical studies have related transverse rms emittance growth in nonuniform beams to changes in the beam density profile, but the time evolution of the process has not been analyzed. Our new approach analyzes the internal motion of the beam and from this obtains the explicit time dependence of the rms emittance. It is shown to reach its peak value explosively in about one quarter of a plasma period. The subsequent behavior depends on the uniformity of the initial density profile. We derive a uniformity criterion that determines whether or not the emittance oscillates periodically and present examples of density profiles for which the emittance returns to its initial value and then continues to oscillate. We discuss a class of continuous initial profiles that lead to discontinuous shocklike behavior (with partial irreversibility of the oscillations) and a class of segmented profiles for which the emittance jumps to its maximum value in one fourth of a plasma period and remains at that value with essentially no further change. (author)

  7. Computational Fluid Dynamics Ventilation Study for the Human Powered Centrifuge at the International Space Station

    Science.gov (United States)

    Son, Chang H.

    2012-01-01

    The Human Powered Centrifuge (HPC) is a facility that is planned to be installed on board the International Space Station (ISS) to enable crew exercises under the artificial gravity conditions. The HPC equipment includes a "bicycle" for long-term exercises of a crewmember that provides power for rotation of HPC at a speed of 30 rpm. The crewmember exercising vigorously on the centrifuge generates the amount of carbon dioxide of about two times higher than a crewmember in ordinary conditions. The goal of the study is to analyze the airflow and carbon dioxide distribution within Pressurized Multipurpose Module (PMM) cabin when HPC is operating. A full unsteady formulation is used for airflow and CO2 transport CFD-based modeling with the so-called sliding mesh concept when the HPC equipment with the adjacent Bay 4 cabin volume is considered in the rotating reference frame while the rest of the cabin volume is considered in the stationary reference frame. The rotating part of the computational domain includes also a human body model. Localized effects of carbon dioxide dispersion are examined. Strong influence of the rotating HPC equipment on the CO2 distribution detected is discussed.

  8. Microwave heating device for internal heating convection experiments, applied to Earth's mantle dynamics.

    Science.gov (United States)

    Surducan, E; Surducan, V; Limare, A; Neamtu, C; Di Giuseppe, E

    2014-12-01

    We report the design, construction, and performances of a microwave (MW) heating device for laboratory experiments with non-contact, homogeneous internal heating. The device generates MW radiation at 2.47 GHz from a commercial magnetron supplied by a pulsed current inverter using proprietary, feedback based command and control hardware and software. Specially designed MW launchers direct the MW radiation into the sample through a MW homogenizer, devised to even the MW power distribution into the sample's volume. An adjustable MW circuit adapts the MW generator to the load (i.e., the sample) placed in the experiment chamber. Dedicated heatsinks maintain the MW circuits at constant temperature throughout the experiment. Openings for laser scanning for image acquisition with a CCD camera and for the cooling circuits are protected by special MW filters. The performances of the device are analyzed in terms of heating uniformity, long term output power stability, and load matching. The device is used for small scale experiments simulating Earth's mantle convection. The 30 × 30 × 5 cm(3) convection tank is filled with a water‑based viscous fluid. A uniform and constant temperature is maintained at the upper boundary by an aluminum heat exchanger and adiabatic conditions apply at the tank base. We characterize the geometry of the convective regime as well as its bulk thermal evolution by measuring the velocity field by Particle Image Velocimetry and the temperature field by using Thermochromic Liquid Crystals.

  9. Microwave heating device for internal heating convection experiments, applied to Earth's mantle dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Surducan, E.; Surducan, V.; Neamtu, C., E-mail: camelia.neamtu@itim-cj.ro [National Institute for Research and Development of Isotopic and Molecular Technologies (INCDTIM), 67-103 Donat St., 400293, Cluj‑Napoca (Romania); Limare, A.; Di Giuseppe, E. [Institut de Physique du Globe de Paris (IPGP), Univ. Paris Diderot, UMR CNRS 7154, 1 rue Jussieu, 75005, Paris (France)

    2014-12-15

    We report the design, construction, and performances of a microwave (MW) heating device for laboratory experiments with non-contact, homogeneous internal heating. The device generates MW radiation at 2.47 GHz from a commercial magnetron supplied by a pulsed current inverter using proprietary, feedback based command and control hardware and software. Specially designed MW launchers direct the MW radiation into the sample through a MW homogenizer, devised to even the MW power distribution into the sample's volume. An adjustable MW circuit adapts the MW generator to the load (i.e., the sample) placed in the experiment chamber. Dedicated heatsinks maintain the MW circuits at constant temperature throughout the experiment. Openings for laser scanning for image acquisition with a CCD camera and for the cooling circuits are protected by special MW filters. The performances of the device are analyzed in terms of heating uniformity, long term output power stability, and load matching. The device is used for small scale experiments simulating Earth's mantle convection. The 30 × 30 × 5 cm{sup 3} convection tank is filled with a water‑based viscous fluid. A uniform and constant temperature is maintained at the upper boundary by an aluminum heat exchanger and adiabatic conditions apply at the tank base. We characterize the geometry of the convective regime as well as its bulk thermal evolution by measuring the velocity field by Particle Image Velocimetry and the temperature field by using Thermochromic Liquid Crystals.

  10. EU internal energy market policy: new dynamics in the Brussels policy game?

    Energy Technology Data Exchange (ETDEWEB)

    Eikeland, Per Ove

    2008-11-15

    The paper analyses the September 2007 European Commission proposal for a third internal energy policy package. It asks if the proposal reflected fundamental changes in the Brussels policy game from 2003, when the existing legislation had been adopted. A multi-level governance approach has inspired this check of alternative propositions. We find that the proposal was primarily the result of greater will on the part of the Commission to pressure unwilling member-state governments. There is also strong evidence that the Commission pursued a new form of multi-level game, pressing non-state agents directly to change the political game at the national level. Our study finally discusses whether different network approaches would add explanatory power to our study, acknowledging that agents working in larger networks could have greater thrust on the Commission. The main conclusion is that EU policy networks have become less stable and more issue-specific, making policy predictions less certain than before. (author).refs.,tab

  11. Analysis of internal shading degree to a prototype of dynamics photovoltaic greenhouse through simulation software

    Directory of Open Access Journals (Sweden)

    Alvaro Marucci

    2015-12-01

    Full Text Available In recent years the use of photovoltaic panels as cover materials for greenhouses developed a great interest due to the state’s incentives obtainable by such applications. Shading caused by these elements inside the structure appears to be often too much for the normal development of agricultural activity. In this study it was analyzed the behaviour of shading caused by the photovoltaic panels inside a prototype of dynamic photovoltaic greenhouse whose particularity lies in the possibility of rotation of the panels along the longitudinal axis. The panels’ rotation allows varying shading degree in function of some parameters such as latitude and the different solar angles. In order to avoid any reflection losses due to imperfect inclination of the photovoltaic panels, 24 highly reflective aluminium mirrors were prepared with the objective of recovering the portion of solar radiation otherwise lost by reflection. For the study it was used the simulation software Autodesk® Ecotect® Analysis which allows to analyse the path of the shadows during the day and throughout the year for any latitude considered. For this study it was analyzed shading with the panels in a horizontal position. It was also analyzed the evolution of the percentage of shading simulating different latitudes. The results obtained show a great variation of the shading degree inside the structure during a single day and during the year. We can conclude that integrating this analysis with the energy balance it is possible to study the behaviour of photovoltaic greenhouses in order to integrate the energy production from renewable energy sources and agricultural production.

  12. Evidence for excited-state intramolecular proton transfer in 4-chlorosalicylic acid from combined experimental and computational studies: Quantum chemical treatment of the intramolecular hydrogen bonding interaction

    Energy Technology Data Exchange (ETDEWEB)

    Paul, Bijan Kumar [Department of Chemistry, University of Calcutta, 92 Acharya Prafulla Chandra Road, Calcutta 700009 (India); Guchhait, Nikhil, E-mail: nikhil.guchhait@rediffmail.com [Department of Chemistry, University of Calcutta, 92 Acharya Prafulla Chandra Road, Calcutta 700009 (India)

    2012-07-25

    Highlights: Black-Right-Pointing-Pointer Experimental and computational studies on the photophysics of 4-chlorosalicylic acid. Black-Right-Pointing-Pointer Spectroscopically established ESIPT reaction substantiated by theoretical calculation. Black-Right-Pointing-Pointer Quantum chemical treatment of IMHB unveils strength, nature and directional nature. Black-Right-Pointing-Pointer Superiority of quantum chemical treatment of H-bond over geometric criteria. Black-Right-Pointing-Pointer Role of H-bond as a modulator of aromaticity. -- Abstract: The photophysical study of a pharmaceutically important chlorine substituted derivative of salicylic acid viz., 4-chlorosalicylic acid (4ClSA) has been carried out by steady-state absorption, emission and time-resolved emission spectroscopy. A large Stokes shifted emission band with negligible solvent polarity dependence marks the spectroscopic signature of excited-state intramolecular proton transfer (ESIPT) reaction in 4ClSA. Theoretical calculation by ab initio and Density Functional Theory methods yields results consistent with experimental findings. Theoretical potential energy surfaces predict the occurrence of proton transfer in S{sub 1}-state. Geometrical and energetic criteria, Atoms-In-Molecule topological parameters, Natural Bond Orbital population analysis have been exploited to evaluate the intramolecular hydrogen bond (IMHB) interaction and to explore its directional nature. The inter-correlation between aromaticity and resonance assisted H-bond is also discussed in this context. Our results unveil that the quantum chemical treatment is a more accurate tool to assess hydrogen bonding interaction in comparison to geometrical criteria.

  13. Intramolecular symmetry-adapted perturbation theory with a single-determinant wavefunction

    Energy Technology Data Exchange (ETDEWEB)

    Pastorczak, Ewa; Prlj, Antonio; Corminboeuf, Clémence, E-mail: clemence.corminboeuf@epfl.ch [Laboratory for Computational Molecular Design, Institut des Sciences et Ingénierie Chimiques, École Polytechnique Fédérale de Lausanne, CH-1015 Lausanne (Switzerland); Gonthier, Jérôme F. [Center for Computational Molecular Science and Technology, School of Chemistry and Biochemistry, School of Computational Science and Engineering, Georgia Institute of Technology, Atlanta, Georgia 30332-0400 (United States)

    2015-12-14

    We introduce an intramolecular energy decomposition scheme for analyzing non-covalent interactions within molecules in the spirit of symmetry-adapted perturbation theory (SAPT). The proposed intra-SAPT approach is based upon the Chemical Hamiltonian of Mayer [Int. J. Quantum Chem. 23(2), 341–363 (1983)] and the recently introduced zeroth-order wavefunction [J. F. Gonthier and C. Corminboeuf, J. Chem. Phys. 140(15), 154107 (2014)]. The scheme decomposes the interaction energy between weakly bound fragments located within the same molecule into physically meaningful components, i.e., electrostatic-exchange, induction, and dispersion. Here, we discuss the key steps of the approach and demonstrate that a single-determinant wavefunction can already deliver a detailed and insightful description of a wide range of intramolecular non-covalent phenomena such as hydrogen bonds, dihydrogen contacts, and π − π stacking interactions. Intra-SAPT is also used to shed the light on competing intra- and intermolecular interactions.

  14. Does the Intramolecular Hydrogen Bond Affect the Spectroscopic Properties of Bicyclic Diazole Heterocycles?

    Directory of Open Access Journals (Sweden)

    Paweł Misiak

    2018-01-01

    Full Text Available The formation of an intramolecular hydrogen bond in pyrrolo[1,2-a]pyrazin-1(2H-one bicyclic diazoles was analyzed, and the influence of N-substitution on HB formation is discussed in this study. B3LYP/aug-cc-pVDZ calculations were performed for the diazole, and the quantum theory of atoms in molecules (QTAIM approach as well as the natural bond orbital (NBO method was applied to analyze the strength of this interaction. It was found that the intramolecular hydrogen bond that closes an extra ring between the C=O proton acceptor group and the CH proton donor, that is, C=O⋯H–C, influences the spectroscopic properties of pyrrolopyrazine bicyclic diazoles, particularly the carbonyl frequencies. The influence of N-substitution on the aromaticity of heterocyclic rings is also discussed in this report.

  15. Intramolecular Charge-Transfer Interaction of Donor-Acceptor-Donor Arrays Based on Anthracene Bisimide.

    Science.gov (United States)

    Iwanaga, Tetsuo; Ogawa, Marina; Yamauchi, Tomokazu; Toyota, Shinji

    2016-05-20

    We designed anthracene bisimide (ABI) derivatives having two triphenylamine (TPA) groups as donor units at the 9,10-positions to form a novel π-conjugated donor-acceptor system. These compounds and their analogues with ethynylene linkers were synthesized by Suzuki-Miyaura and Sonogashira coupling reactions, respectively. In UV-vis spectra, the linker-free derivatives showed broad absorption bands arising from intramolecular charge-transfer interactions. Introducing ethynylene linkers resulted in a considerable red shift of the absorption bands. In fluorescence spectra, the ethynylene derivatives showed intense emission bands at 600-650 nm. Their photophysical and electrochemical properties were compared with those of the corresponding mono TPA derivatives on the basis of theoretical calculations and cyclic voltammetry to evaluate the intramolecular electronic interactions between the donor and acceptor units.

  16. Fast and versatile microwave-assisted intramolecular Heck reaction in peptide macrocyclization using microwave energy.

    Science.gov (United States)

    Byk, Gerardo; Cohen-Ohana, Mirit; Raichman, Daniel

    2006-01-01

    We have revisited the intramolecular Heck reaction and investigated the microwave-assisted macrocyclization on preformed peptides using a model series of ring-varying peptides acryloyl-Gly-[Gly](n)-Phe(4-I)NHR; n = 0-4. The method was applied to both solution and solid supported cyclizations. We demonstrate that the intramolecular Heck reaction can be performed in peptides both in solution and solid support using a modified domestic microwave within 1 to 30 minutes in DMF under reflux with moderate yields ranging from 15 to 25% for a scale between 2-45 mg of linear precursors. The approach was applied to the synthesis of a constrained biologically relevant peptidomimetic bearing an Arg-Gly-Asp (RGD) sequence. These results make the microwave-assisted Heck reaction an attractive renovated approach for peptidomimetics. Copyright 2006 Wiley Periodicals, Inc.

  17. Dual fluorescence of excited state intra-molecular proton transfer of HBFO: mechanistic understanding, substituent and solvent effects.

    Science.gov (United States)

    Yang, Wenjing; Chen, Xuebo

    2014-03-07

    A combined approach of the multiconfigurational perturbation theory with the Rice-Ramsperger-Kassel-Marcus methodology has been employed to calculate the minimum potential energy profiles and the rates of excited state intra-molecular proton transfer (ESIPT) for the WOLED material molecule of HBFO and its four meta- or para-substituted compounds in gas phase, acetonitrile and cyclohexane solvents. The kinetic control for these reactions is quantitatively determined and extensively studied on the basis of the accurate potential energy surfaces when the thermodynamic factor associated with the free energy change becomes negligible in the case of the existence of a significant barrier in the ESIPT process. These computational efforts contribute to a deep understanding of the ESIPT mechanism, dual emission characteristics, kinetic controlling factor, substituent and solvent effects for these material molecules. The white light emission is generated by the establishment of dynamic equilibrium between enol and keto forms in the charge transfer excited SCT((1)ππ*) state. The performance of white light emission is quantitatively demonstrated to be mainly sensitive to the molecular tailoring approach of the electronic properties of meta- or para- substituents by the modulation of the forward/backward ESIPT rate ratio. The quality of white light emission is slightly tunable through its surrounding solvent environment. These computational results will provide a useful strategy for the molecular design of OLED and WOLED materials.

  18. Modeling and computations of the intramolecular electron transfer process in the two-heme protein cytochrome em>c>4

    DEFF Research Database (Denmark)

    Natzmutdinov, Renat R.; Bronshtein, Michael D.; Zinkicheva, Tamara T.

    2012-01-01

    force were determined using dielectric continuum models. We then calculated the electronic transmission coefficient of the intramolecular ET rate using perturbation theory combined with the electronic wave functions determined by the DFT calculations for different heme group orientations and Fe...

  19. Intramolecular Dynamics: A Study of Molecules at High Levels of Vibrational Excitation.

    Science.gov (United States)

    1988-05-27

    aareemlent stith the photoa.couxueC rexults.,I4 % obintied t r iii pfii ioaCOI it tic tveaxu retntsx." Si ne thle xhoxs xthat Iii the I ott fi nence...t 0 200 400 ns 6000 between pump and probe pulse for CH3 CHF2 at 660 Pa. Infrared excitation: 10.6 pim P(20) line, 0.5 ns pulse with average fluence

  20. Intramolecular dynamics due to electron transitions: from photoelectron spectroscopy to Femtochemistry

    International Nuclear Information System (INIS)

    Gadzuk, J.W.

    1999-01-01

    Select spectroscopic and chemical physics problems associated with atomic motion triggered by electronic transitions are the topics of this paper. The story starts with the initial stimulation provided by Dick Brundle's photoelectron spectroscopy studies of adsorbed molecules and continues to contemporary examples in photoelectron spectroscopy and Femtochemistry, all of which are theoretically modelled within a unified framework of time-dependent, driven oscillators and decaying states. (Copyright (c) 1999 Elsevier Science B.V., Amsterdam. All rights reserved.)

  1. The evolution of young HII regions. I. Continuum emission and internal dynamics

    Science.gov (United States)

    Klaassen, P. D.; Johnston, K. G.; Urquhart, J. S.; Mottram, J. C.; Peters, T.; Kuiper, R.; Beuther, H.; van der Tak, F. F. S.; Goddi, C.

    2018-04-01

    Context. High-mass stars form in much richer environments than those associated with isolated low-mass stars, and once they reach a certain mass, produce ionised (HII) regions. The formation of these pockets of ionised gas are unique to the formation of high-mass stars (M > 8 M⊙), and present an excellent opportunity to study the final stages of accretion, which could include accretion through the HII region itself. Aim. This study of the dynamics of the gas on both sides of these ionisation boundaries in very young HII regions aims to quantify the relationship between the HII regions and their immediate environments. Methods: We present high-resolution ( 0.5″) ALMA observations of nine HII regions selected from the red MSX source survey with compact radio emission and bolometric luminosities greater than 104 L⊙. We focus on the initial presentation of the data, including initial results from the radio recombination line H29α, some complementary molecules, and the 256 GHz continuum emission. Results: Of the six (out of nine) regions with H29α detections, two appear to have cometary morphologies with velocity gradients across them, and two appear more spherical with velocity gradients suggestive of infalling ionised gas. The remaining two were either observed at low resolution or had signals that were too weak to draw robust conclusions. We also present a description of the interactions between the ionised and molecular gas (as traced by CS (J = 5 - 4)), often (but not always) finding the HII region had cleared its immediate vicinity of molecules. Conclusions: Of our sample of nine, the observations of the two clusters expected to have the youngest HII regions (from previous radio observations) are suggestive of having infalling motions in the H29α emission, which could be indicative of late stage accretion onto the stars despite the presence of an HII region. Table A.2 is also available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (http://130

  2. Iron(II)-catalyzed intramolecular aminohydroxylation of olefins with functionalized hydroxylamines.

    Science.gov (United States)

    Liu, Guan-Sai; Zhang, Yong-Qiang; Yuan, Yong-An; Xu, Hao

    2013-03-06

    A diastereoselective aminohydroxylation of olefins with a functionalized hydroxylamine is catalyzed by new iron(II) complexes. This efficient intramolecular process readily affords synthetically useful amino alcohols with excellent selectivity (dr up to > 20:1). Asymmetric catalysis with chiral iron(II) complexes and preliminary mechanistic studies reveal an iron nitrenoid is a possible intermediate that can undergo either aminohydroxylation or aziridination, and the selectivity can be controlled by careful selection of counteranion/ligand combinations.

  3. Towards single-molecule detection of intramolecular exciplexes: Photophysics of a benzanthrone derivative

    Energy Technology Data Exchange (ETDEWEB)

    Hattori, Akifumi [Graduate School of Bio-Applications and Systems Engineering (BASE), Tokyo University of Agriculture and Technology, 2-24-16 Naka-machi, Koganei, Tokyo, 184-8588 (Japan); Department of Organic and Polymeric Materials, Tokyo Institute of Technology, Ookayama 2-12-1-S8, Meguro-ku, Tokyo, 152-8552 (Japan); Sato, Hisaya [Graduate School of Bio-Applications and Systems Engineering (BASE), Tokyo University of Agriculture and Technology, 2-24-16 Naka-machi, Koganei, Tokyo, 184-8588 (Japan); Vacha, Martin [Department of Organic and Polymeric Materials, Tokyo Institute of Technology, Ookayama 2-12-1-S8, Meguro-ku, Tokyo, 152-8552 (Japan)]. E-mail: vacha@op.titech.ac.jp

    2007-01-15

    We report luminescence study of intramolecular exciplexes based on an aminobenzanthrone derivative, dimethyl-amino-N-acetyl-3-aminobenzanthrone (BDA). The BDA compound shows strong dependence of the exciplex emission band intensity on the solvent dielectric function and moderate dependence on its viscosity. The exciplex emission mechanism is discussed in view of the unusual solvent polarity dependence and solvent-dependent excited state lifetimes. Preliminary results on single-molecule detection in polymer films are also presented.

  4. Towards single-molecule detection of intramolecular exciplexes: Photophysics of a benzanthrone derivative

    International Nuclear Information System (INIS)

    Hattori, Akifumi; Sato, Hisaya; Vacha, Martin

    2007-01-01

    We report luminescence study of intramolecular exciplexes based on an aminobenzanthrone derivative, dimethyl-amino-N-acetyl-3-aminobenzanthrone (BDA). The BDA compound shows strong dependence of the exciplex emission band intensity on the solvent dielectric function and moderate dependence on its viscosity. The exciplex emission mechanism is discussed in view of the unusual solvent polarity dependence and solvent-dependent excited state lifetimes. Preliminary results on single-molecule detection in polymer films are also presented

  5. Origin of Exo/Endo Selectivity in the Intramolecular Diels-Alder Reaction

    International Nuclear Information System (INIS)

    Yan, Shihai; Ryu, Do Hyun; Lee, Jin Yong

    2010-01-01

    The stereoselectivity of the intramolecular Diels-Alder reactions of 1 and its derivatives were investigated by ab initio calculations. The stereoselectivity mainly originates from the steric repulsion and the orbital interactions. The additional s-cis and s-trans conformations by introducing the carbonyl group at the neighbor of diene or dienophile may change the stereoselectivity, hence this kind of substitution can be utilized for stereoselective asymmetric synthesis

  6. Fe(II)/Fe(III)-Catalyzed Intramolecular Didehydro-Diels-Alder Reaction of Styrene-ynes.

    Science.gov (United States)

    Mun, Hyeon Jin; Seong, Eun Young; Ahn, Kwang-Hyun; Kang, Eun Joo

    2018-02-02

    The intramolecular didehydro-Diels-Alder reaction of styrene-ynes was catalyzed by Fe(II) and Fe(III) to produce various naphthalene derivatives under microwave heating conditions. Mechanistic calculations found that the Fe(II) catalyst activates the styrenyl diene in an inverse-electron-demand Diels-Alder reaction, and the consecutive dehydrogenation reaction can be promoted by either Fe(II)-catalyzed direct dehydrogenation or an Fe(III)-catalyzed rearomatization/dehydrogenation pathway.

  7. Photoinduced intramolecular substitution reaction of aryl halide with carbonyl oxygen of amide group

    CERN Document Server

    Park, Y T; Kim, M S; Kwon, J H

    2002-01-01

    Photoreaction of N-(o-halophenyl)acetamide in basic acetonitrile produces an intramolecular substituted product, 2-methylbenzoxazole in addition to reduced product, acetanilide, whereas photoreaction of N-(o-halobenzyl)acetamide affords a reduced product, N-benzylacetamide only. On the basis of preparative reaction, kinetics, and UV/vis absorption behavior, an electrophilic aromatic substitution of aryl halide with oxygen of its amide bond are proposed.

  8. Surprisingly Mild Enolate-Counterion-Free Pd(0)-Catalyzed Intramolecular Allylic Alkylations

    DEFF Research Database (Denmark)

    Madec, David; Prestat, Guillaume; Martini, Elisabetta

    2005-01-01

    Palladium-catalyzed intramolecular allylic alkylations of unsaturated EWG-activated amides can take place under phase-transfer conditions or in the presence of a crown ether. These new reaction conditions are milder and higher yielding than those previously reported. A rationalization for such an...... for such an unexpected result is put forth and validated by DFT-B3LYP calculations. The results suggest cyclization via a counterion-free (E)-enolate TS....

  9. Some kinetic and spectroscopic evidence on intramolecular relaxation processes in polyatomic molecules

    International Nuclear Information System (INIS)

    Quack, M.

    1983-01-01

    The description and definition of intramolecular vibrational relaxation processes is discussed within the framework of the quantum mechanical and statistical mechanical equations of motion. The evidence from quite different experimental sources is summarized under the common aspect of vibrational relaxation. Although much of the evidence remains ambiguous, there is good indication that a localized vibrational excitation relaxes typically in 0.1 to 10 picoseconds, which is long compared to many optical and reactive processes

  10. Electron capture dissociation proceeds with a low degree of intramolecular migration of peptide amide hydrogens

    DEFF Research Database (Denmark)

    Rand, Kasper D; Adams, Christopher M; Zubarev, Roman A

    2008-01-01

    scrambling) that occurs during vibrational excitation of gas-phase ions. Unlike traditional collisional ion activation, electron capture dissociation (ECD) is not associated with substantial vibrational excitation. We investigated the extent of intramolecular backbone amide hydrogen (1H/2H) migration upon...... ECD using peptides with a unique selective deuterium incorporation. Our results show that only limited amide hydrogen migration occurs upon ECD, provided that vibrational excitation prior to the electron capture event is minimized. Peptide ions that are excessively vibrationally excited...

  11. Antimalarial peroxides: the first intramolecular 1,2,4,5-tetraoxane

    Directory of Open Access Journals (Sweden)

    BOGDAN A. SOLAJA

    2002-07-01

    Full Text Available An intramolecular steroidal 1,2,4,5-tetraoxane has been synthesised in six steps starting from methyl 3-oxo-7a,12a-diacetoxy-5b-cholan-24-oate. The synthesised 1,2,4,5-tetraoxane has moderate in vitro antimalarial activity against P. falciparum strains (IC50 (D6 = 0.35 mg/mL; IC50 (W2 = 0.29 mg/mL.

  12. Ductile Glass of Polyrotaxane Toughened by Stretch-Induced Intramolecular Phase Separation.

    Science.gov (United States)

    Kato, Kazuaki; Nemoto, Kaito; Mayumi, Koichi; Yokoyama, Hideaki; Ito, Kohzo

    2017-09-27

    A new class of ductile glasses is created from a thermoplastic polyrotaxane. The hard glass, which has a Young's modulus of 1 GPa, shows crazing, necking, and strain hardening with a total elongation of 330%. Stress concentration is prevented through a unique stretch-induced intramolecular phase separation of the cyclic components and the exposed backbone. In situ synchrotron X-ray scattering studies indicate that the backbone polymer chains slip through the cyclic components in the regions where the stress is concentrated.

  13. Intramolecular Azide to Alkene Cycloadditions for the Construction of Pyrrolobenzodiazepines and Azetidino-Benzodiazepines

    Directory of Open Access Journals (Sweden)

    Karl Hemming

    2014-10-01

    Full Text Available The coupling of proline- and azetidinone-substituted alkenes to 2-azidobenzoic and 2-azidobenzenesulfonic acid gives precursors that undergo intramolecular azide to alkene 1,3-dipolar cycloadditions to give imine-, triazoline- or aziridine-containing pyrrolo[1,4]benzodiazepines (PBDs, pyrrolo[1,2,5]benzothiadiazepines (PBTDs, and azetidino[1,4]benzodiazepines. The imines and aziridines are formed after loss of nitrogen from a triazoline cycloadduct. The PBDs are a potent class of antitumour antibiotics.

  14. Photoinduced intramolecular substitution reaction of aryl halide with carbonyl oxygen of amide group

    Energy Technology Data Exchange (ETDEWEB)

    Park, Yong Tae; Song, Myong Geun; Kim, Moon Sub; Kwon, Jeong Hee [Kyungpook National Univ., Daegu (Korea, Republic of)

    2002-09-01

    Photoreaction of N-(o-halophenyl)acetamide in basic acetonitrile produces an intramolecular substituted product, 2-methylbenzoxazole in addition to reduced product, acetanilide, whereas photoreaction of N-(o-halobenzyl)acetamide affords a reduced product, N-benzylacetamide only. On the basis of preparative reaction, kinetics, and UV/vis absorption behavior, an electrophilic aromatic substitution of aryl halide with oxygen of its amide bond are proposed.

  15. Photoinduced intramolecular substitution reaction of aryl halide with carbonyl oxygen of amide group

    International Nuclear Information System (INIS)

    Park, Yong Tae; Song, Myong Geun; Kim, Moon Sub; Kwon, Jeong Hee

    2002-01-01

    Photoreaction of N-(o-halophenyl)acetamide in basic acetonitrile produces an intramolecular substituted product, 2-methylbenzoxazole in addition to reduced product, acetanilide, whereas photoreaction of N-(o-halobenzyl)acetamide affords a reduced product, N-benzylacetamide only. On the basis of preparative reaction, kinetics, and UV/vis absorption behavior, an electrophilic aromatic substitution of aryl halide with oxygen of its amide bond are proposed

  16. The Intramolecular Diels–Alder Reaction of Tryptamine-Derived Zincke Aldehydes Is a Stepwise Process

    OpenAIRE

    Pham, Hung V.; Martin, David B. C.; Vanderwal, Christopher D.; Houk, K. N.

    2012-01-01

    Computational studies show that the base-mediated intramolecular Diels–Alder of tryptamine-derived Zincke aldehydes, used as a key step in the synthesis of the Strychnos alkaloids norfluorocurarine and strychnine, proceeds via a stepwise pathway. The experimentally determined importance of a potassium counterion in the base is explained by its ability to preorganize the Zincke aldehyde diene in an s-cis conformation suitable to bicyclization. Computation also supports the thermodynamic import...

  17. An intramolecular inverse electron demand Diels–Alder approach to annulated α-carbolines

    Directory of Open Access Journals (Sweden)

    Zhiyuan Ma

    2012-06-01

    Full Text Available Intramolecular inverse electron demand cycloadditions of isatin-derived 1,2,4-triazines with acetylenic dienophiles tethered by amidations or transesterifications proceed in excellent yields to produce lactam- or lactone-fused α-carbolines. Beginning with various isatins and alkynyl dienophiles, a pilot-scale library of eighty-eight α-carbolines was prepared by using this robust methodology for biological evaluation.

  18. Photodynamics of oxybenzone sunscreen: Nonadiabatic dynamics simulations

    Energy Technology Data Exchange (ETDEWEB)

    Li, Chun-Xiang; Guo, Wei-Wei; Xie, Bin-Bin; Cui, Ganglong, E-mail: ganglong.cui@bnu.edu.cn [Key Laboratory of Theoretical and Computational Photochemistry, Ministry of Education, College of Chemistry, Beijing Normal University, Beijing 100875 (China)

    2016-08-21

    Herein we have used combined static electronic structure calculations and “on-the-fly” global-switching trajectory surface-hopping dynamics simulations to explore the photochemical mechanism of oxybenzone sunscreen. We have first employed the multi-configurational CASSCF method to optimize minima, conical intersections, and minimum-energy reaction paths related to excited-state intramolecular proton transfer (ESIPT) and excited-state decays in the {sup 1}ππ{sup ∗}, {sup 1}nπ{sup ∗}, and S{sub 0} states (energies are refined at the higher MS-CASPT2 level). According to the mapped potential energy profiles, we have identified two ultrafast excited-state deactivation pathways for the initially populated {sup 1}ππ{sup ∗} system. The first is the diabatic ESIPT process along the {sup 1}ππ{sup ∗} potential energy profile. The generated {sup 1}ππ{sup ∗} keto species then decays to the S{sub 0} state via the keto {sup 1}ππ{sup ∗}/gs conical intersection. The second is internal conversion to the dark {sup 1}nπ{sup ∗} state near the {sup 1}ππ{sup ∗} /{sup 1}nπ{sup ∗} crossing point in the course of the diabatic {sup 1}ππ{sup ∗} ESIPT process. Our following dynamics simulations have shown that the ESIPT and {sup 1}ππ{sup ∗} → S{sub 0} internal conversion times are 104 and 286 fs, respectively. Finally, our present work demonstrates that in addition to the ESIPT process and the {sup 1}ππ{sup ∗} → S{sub 0} internal conversion in the keto region, the {sup 1}ππ{sup ∗} → {sup 1}nπ{sup ∗} internal conversion in the enol region plays as well an important role for the excited-state relaxation dynamics of oxybenzone.

  19. PREFACE: 10th International Conference on Clustering Aspects of Nuclear Structure and Dynamics (CLUSTER'12)

    Science.gov (United States)

    Lovas, R. G.; Dombrádi, Zs; Kiss, G. G.; Kruppa, A. T.; Lévai, G.

    2013-04-01

    , but we had some invited talks even in the parallel sessions. Written versions of 86 talks have been submitted. Quite a number of the speakers have modified the title of their talk in the written version. To keep the correspondence between the Programme list and the written papers, we have accordingly changed the titles in the Programme list as well. The papers are arranged according to their subjects, without regard to whether they were delivered in a plenary or in a parallel session. There was a talk classified wrongly; this is now classified correctly. In the Programme list and in the list of the papers submitted the names are those of the speakers. You can read in the Opening Address that, by ruling of the organizing institution, no members of the Debrecen Institute of Nuclear Research were selected as invited speakers and no contributions were accepted from them. We doubted the wisdom of this rigour ourselves, and I think the criticism we received for it is justifiable. The success of a conference depends primarily on the speakers. In retrospect, we can say that this conference was extremely successful, and that is owing to the great many wonderful talks delivered. This reflects very well on the present status of the field as well as on the work of the International Advisory Board, which proposed the list of excellent speakers. The Japanese dominance characteristic of all cluster conferences has only been complained about by some of the Japanese who came to Europe primarily to learn things that they could not learn at home. We would like to express our gratitude to our sponsors: the Hungarian Academy of Sciences the Paks Nuclear Power Ltd HMP Logic Ltd International Workshop for Theoretical Physics(Budapest) We were also supported indirectly by a JSPS-MTA bilateral cooperation project, which made it possible for five Japanese colleagues to participate. It just remains to be announced that the next, number 11 in this series of conferences, will be held in Naples in

  20. Formation of benzo[f]-1-indanone frameworks by regulable intramolecular annulations of gem-dialkylthio trienynes.

    Science.gov (United States)

    Fang, Zhongxue; Liu, Ying; Barry, Badru-Deen; Liao, Peiqiu; Bi, Xihe

    2015-02-20

    An atom-economic route to benzo[f]-1-indanone frameworks has been developed starting from the readily available gem-dialkylthio trienynes by intramolecular annulations. The chemoselectivity of the intramolecular cyclizations can be regulated by both the base and the type of gas atmosphere used in the reaction, thus allowing the divergent synthesis of the corresponding functionalized benzo[f]-1-indanones in good to excellent yields.

  1. Quantitative analysis of intramolecular exciplex and electron transfer in a double-linked zinc porphyrin-fullerene dyad.

    Science.gov (United States)

    Al-Subi, Ali Hanoon; Niemi, Marja; Tkachenko, Nikolai V; Lemmetyinen, Helge

    2012-10-04

    Photoinduced charge transfer in a double-linked zinc porphyrin-fullerene dyad is studied. When the dyad is excited at the absorption band of the charge-transfer complex (780 nm), an intramolecular exciplex is formed, followed by the complete charge separated (CCS) state. By analyzing the results obtained from time-resolved transient absorption and emission decay measurements in a range of solvents with different polarities, we derived a dependence between the observable lifetimes and internal parameters controlling the reaction rate constants based on the semiquantum Marcus electron-transfer theory. The critical value of the solvent polarity was found to be ε(r) ≈ 6.5: in solvents with higher dielectric constants, the energy of the CCS state is lower than that of the exciplex and the relaxation takes place via the CCS state predominantly, whereas in solvents with lower polarities the energy of the CCS state is higher and the exciplex relaxes directly to the ground state. In solvents with moderate polarities the exciplex and the CCS state are in equilibrium and cannot be separated spectroscopically. The degree of the charge shift in the exciplex relative to that in the CCS state was estimated to be 0.55 ± 0.02. The electronic coupling matrix elements for the charge recombination process and for the direct relaxation of the exciplex to the ground state were found to be 0.012 ± 0.001 and 0.245 ± 0.022 eV, respectively.

  2. THE ROLE OF INTRAMOLECULAR TIES ENERGY IN THE PYROLYSIS PROCESS OF PET

    Directory of Open Access Journals (Sweden)

    P. Iu. Salikov

    2014-01-01

    Full Text Available Summary. Recycling plastic waste to focus on. The main type of used products made of polyethylene terephthalate (PET is a container from the various types of beverages. There was considered a possibility of waste of PET (bottles, bottles, packaging containers by pyrolysis. Most of the proposed methods are not suitable for recycling (recycling of waste consumption contamination. Purpose - to develop technological foundations and optimum modes waste PET to obtain useful secondary products, taking into account the energy of chemical intramolecular bonds. Applied scientific basis of recycling PET into useful forms of secondary products, in particular the establishment of the collapse of the intramolecular bonds, depending on the temperature of the pyrolysis method of mathematical processing - differentiation of polynomial equations change in the degree of pyrolysis temperature-dependent. The optimum modes of processing. The block diagram of apparatus for processing contaminated waste PET pyrolysis methods of control processing in accordance with the specified composition of secondary products. The possibility of controlling the amount and types of fuel components of secondary products due to measurable parameters of the pyrolysis process. The effective temperature pyrolysis of waste PET with the CCA-tures energy intramolecular bonds.

  3. Unique Intramolecular Electronic Communications in Mono-ferrocenylpyrimidine Derivatives: Correlation between Redox Properties and Structural Nature

    International Nuclear Information System (INIS)

    Xiang, Debo; Noel, Jerome; Shao, Huibo; Dupas, Georges; Merbouh, Nabyl; Yu, Hua-Zhong

    2015-01-01

    Highlights: • Unique intramolecular electronic communications (electron withdrawing and π-bond delocalization effects) exist in the mono-ferrocenylpyrimidine derivatives. • The redox potential shift correlates the pyrimidine ring torsion angle with the extent of electron delocalization. • The correlation between redox properties and structural nature in mono-ferrocenylpyrimidine derivatives is evident. - Abstract: The correlation between redox properties and structural nature in a complete set of mono-ferrocenylpyrimidine derivatives (2-ferrocenylpyrimidine, 2-FcPy; 4-ferrocenylpyrimidine, 4-FcPy; 5-ferrocenylpyrimidine, 5-FcPy) was evaluated by investigating the intramolecular electronic communications. Both conventional electrochemical measurements in organic solvents and thin-film voltammetric studies of these compounds were carried out. It was discovered that their formal potentials are significantly different from each other, and shift negatively in the order of 4-FcPy > 5-FcPy > 2-FcPy. This result suggests that the intramolecular electronic communication is dictated by the delocalization effect of the π-bonding systems in 2-FcPy, and that the electron-withdrawing effect of the nitrogen atoms in the pyrimidine ring plays the key role in 4-FcPy and 5-FcPy. The single crystal X-ray structure analyis and Density Functional Theory (DFT) calculation provided additional evidence (e.g., different torsion angles between the cyclopentadienyl and pyrimidine rings) to support the observed correlation between the redox properties and structural nature

  4. Light induced intramolecular electron and energy transfer events in rigidly linked borondipyrromethene: Corrole Dyad

    Energy Technology Data Exchange (ETDEWEB)

    Giribabu, Lingamallu, E-mail: giribabu@iict.res.in [Inorganic & Physical Chemistry Division, CSIR-Indian Institute of Chemical Technology, Tarnaka, Hyderabad 500007, Telangana (India); Jain, Kanika [Department of Chemistry, School of Chemical Sciences & Pharmacy, Central University of Rajasthan, Kishangarh, Dist. Ajmer, Rajasthan 305817 (India); Sudhakar, Kolanu; Duvva, Naresh [Inorganic & Physical Chemistry Division, CSIR-Indian Institute of Chemical Technology, Tarnaka, Hyderabad 500007, Telangana (India); Chitta, Raghu, E-mail: raghuchitta@curaj.ac.in [Department of Chemistry, School of Chemical Sciences & Pharmacy, Central University of Rajasthan, Kishangarh, Dist. Ajmer, Rajasthan 305817 (India)

    2016-09-15

    We have designed and synthesized a photo-induced energy/electron donor–acceptor conjugate comprising of corrole linked to BODIPY at the 5-position via ester linkage. The dyad was characterized by elemental analysis, MALDI-MS, UV-Visible, {sup 1}H NMR fluorescence spectroscopy (steady-state and time-resolved) as well as electrochemical methods. A comparison of the UV–visible and {sup 1}H NMR spectra of the dyad with those of the corresponding individual model compounds (i.e., BODIPY-CO{sub 2}H and BPFC-OH) reveal that there exist minimum π–π interactions between BODIPY and corrole π-planes. Quenched emission of BODIPY and corrole part of the dyad has been observed in five different solvents. Excitation spectral data provided evidence for an intramolecular excitation energy transfer (EET) from the singlet BODIPY to the corrole and an intramolecular photoinduced electron transfer (PET) from singlet state of corrole to ground state of BODIPY. Detailed analysis of the data suggests that Forster's dipole–dipole mechanism does not adequately explain this energy transfer but, an electron exchange mediated mechanism can, in principle, contribute to the intramolecular EET.

  5. Regulation of interleukin-4 signaling by extracellular reduction of intramolecular disulfides

    International Nuclear Information System (INIS)

    Curbo, Sophie; Gaudin, Raphael; Carlsten, Mattias; Malmberg, Karl-Johan; Troye-Blomberg, Marita; Ahlborg, Niklas; Karlsson, Anna; Johansson, Magnus; Lundberg, Mathias

    2009-01-01

    Interleukin-4 (IL-4) contains three structurally important intramolecular disulfides that are required for the bioactivity of the cytokine. We show that the cell surface of HeLa cells and endotoxin-activated monocytes can reduce IL-4 intramolecular disulfides in the extracellular space and inhibit binding of IL-4 to the IL-4Rα receptor. IL-4 disulfides were in vitro reduced by thioredoxin 1 (Trx1) and protein disulfide isomerase (PDI). Reduction of IL-4 disulfides by the cell surface of HeLa cells was inhibited by auranofin, an inhibitor of thioredoxin reductase that is an electron donor to both Trx1 and PDI. Both Trx1 and PDI have been shown to be located at the cell surface and our data suggests that these enzymes are involved in catalyzing reduction of IL-4 disulfides. The pro-drug N-acetylcysteine (NAC) that promotes T-helper type 1 responses was also shown to mediate the reduction of IL-4 disulfides. Our data provides evidence for a novel redox dependent pathway for regulation of cytokine activity by extracellular reduction of intramolecular disulfides at the cell surface by members of the thioredoxin enzyme family.

  6. Intramolecular electron transfer through a bridging carboxylate group coordinated to two cobalt(III)-ions

    International Nuclear Information System (INIS)

    Wieghardt, K.

    1978-01-01

    Reduction of the binuclear μ-p-nitrobenzoato -di-μ-hydroxo -bis[triammine cobalt(III)] cation with (CH 3 ) 2 COH radicals yields a radical cation with the p-nitrobenzoato radical being coordinated to two cobalt(III) ions at the carboxylic group. The unprotonated form of this species undergoes intramolecular electron transfer producing Co(II) (k = (3.3 +- 0.3). x 10 3 s -1 ). The role of the carboxylate group in the intramolecular electron transfer process is tentatively assessed in terms of an intramolecular outer-sphere reaction because of lack of overlap of the donor orbitals (π) and the acceptor orbital (sigma). The protonated form of the radical cation (pKsub(a) = 2.5) disproportionates via a bimolecular process without production of Co(II). The effect of two coordinated Co(III) ions as compared to only one on the properties of the nitrobenzoate radical anion are discussed. (orig.) 891 HK 892 GM [de

  7. Intramolecular Hydrogen Bonding and Conformational Preferences of Arzanol—An Antioxidant Acylphloroglucinol

    Directory of Open Access Journals (Sweden)

    Liliana Mammino

    2017-08-01

    Full Text Available Arzanol is a naturally-occurring prenylated acylphloroglucinol isolated from Helichrysum italicum and exhibiting anti-oxidant, antibiotic and antiviral activities. The molecule contains an α-pyrone moiety attached to the phloroglucinol moiety through a methylene bridge. The presence of several hydrogen bond donor or acceptor sites makes intramolecular hydrogen bonding patterns the dominant stabilising factor. Conformers with all the possible different hydrogen bonding patterns were calculated at the HF/6-31G(d,p and DFT/B3LYP/6-31+G(d,p levels with fully relaxed geometry in vacuo and in three solvents—chloroform, acetonitrile and water (these levels being chosen to enable comparisons with previous studies on acylphloroglucinols. Calculations in solution were performed with the Polarisable Continuum Model. The results show that the lowest energy conformers have the highest number of stronger intramolecular hydrogen bonds. The influence of intramolecular hydrogen bonding patterns on the other molecular properties is also analysed.

  8. Impact of undamped and damped intramolecular vibrations on the efficiency of photosynthetic exciton energy transfer

    Science.gov (United States)

    Juhász, Imre Benedek; Csurgay, Árpád I.

    2018-04-01

    In recent years, the role of molecular vibrations in exciton energy transfer taking place during the first stage of photosynthesis attracted increasing interest. Here, we present a model formulated as a Lindblad-type master equation that enables us to investigate the impact of undamped and especially damped intramolecular vibrational modes on the exciton energy transfer, particularly its efficiency. Our simulations confirm the already reported effects that the presence of an intramolecular vibrational mode can compensate the energy detuning of electronic states, thus promoting the energy transfer; and, moreover, that the damping of such a vibrational mode (in other words, vibrational relaxation) can further enhance the efficiency of the process by generating directionality in the energy flow. As a novel result, we show that this enhancement surpasses the one caused by pure dephasing, and we present its dependence on various system parameters (time constants of the environment-induced relaxation and excitation processes, detuning of the electronic energy levels, frequency of the intramolecular vibrational modes, Huang-Rhys factors, temperature) in dimer model systems. We demonstrate that vibrational-relaxation-enhanced exciton energy transfer (VREEET) is robust against the change of these characteristics of the system and occurs in wide ranges of the investigated parameters. With simulations performed on a heptamer model inspired by the Fenna-Matthews-Olson (FMO) complex, we show that this mechanism can be even more significant in larger systems at T = 300 K. Our results suggests that VREEET might be prevalent in light-harvesting complexes.

  9. Intramolecular BSSE and dispersion affect the structure of a dipeptide conformer

    Science.gov (United States)

    Hameed, Rabia; Khan, Afsar; van Mourik, Tanja

    2018-05-01

    B3LYP and MP2 calculations with the commonly-used 6-31+G(d) basis set predict qualitatively different structures for the Tyr-Gly conformer book1, which is the most stable conformer identified in a previous study. The structures differ mainly in the ψtyr Ramachandran angle (138° in the B3LYP structure and 120° in the MP2 structure). The causes for the discrepant structures are attributed to missing dispersion in the B3LYP calculations and large intramolecular BSSE in the MP2 calculations. The correct ψtyr value is estimated to be 130°. The MP2/6-31+G(d) profile identified an additional conformer, not present on the B3LYP surface, with a ψtyr value of 96° and a more folded structure. This minimum is, however, likely an artefact of large intramolecular BSSE values. We recommend the use of basis sets of at least quadruple-zeta quality in density functional theory (DFT), DFTaugmented with an empirical dispersion term (DFT-D) and second-order Møller-Plesset perturbation theory (MP2 ) calculations in cases where intramolecular BSSE is expected to be large.

  10. Dynamics

    CERN Document Server

    Goodman, Lawrence E

    2001-01-01

    Beginning text presents complete theoretical treatment of mechanical model systems and deals with technological applications. Topics include introduction to calculus of vectors, particle motion, dynamics of particle systems and plane rigid bodies, technical applications in plane motions, theory of mechanical vibrations, and more. Exercises and answers appear in each chapter.

  11. Shenzhen International Low Carbon City in Development: Practice of Low Carbon Planning Technology Strategy Based on Dynamic Demands

    Institute of Scientific and Technical Information of China (English)

    Yu; Han; Li; Caige

    2016-01-01

    Targeted at the dynamic demands in the rapid urban construction, the planning technology strategy of the Shenzhen International Low Carbon City studies the fl exible index model based on carbon emission evaluation, and adopts rolling development and micro-circulation construction mode to achieve quick returns with small investment. Meanwhile, it also evaluates the application of low carbon technology and gives feedback in time, so as to constantly optimize and complete the low carbon city planning. In detail, it involves industrial planning, ecological restoration, transport planning, energy resource planning, architectural design, etc., for which appropriate approaches are selected according to the principle of rolling development of unit cells and based on different requirements of different stages. The quick-response and fl exible technology system can help the low carbon city to choose an appropriate technology strategy in line with its own characteristics in the start-up stage and rapid development, thus realizing the sustainable leap-forward development and providing reference for other similar regions.

  12. Shenzhen International Low Carbon City in Development: Practice of Low Carbon Planning Technology Strategy Based on Dynamic Demands

    Institute of Scientific and Technical Information of China (English)

    Yu Han; Li Caige

    2016-01-01

    Targeted at the dynamic demands in the rapid urban construction,the planning technology strategy of the Shenzhen International Low Carbon City studies the flexible index model based on carbon emission evaluation,and adopts rolling development and micro-circulation construction mode to achieve quick returns with small investment.Meanwhile,it also evaluates the application of low carbon technology and gives feedback in time,so as to constantly optimize and complete the low carbon city planning.In detail,it involves industrial planning,ecological restoration,transport planning,energy resource planning,architectural design,etc.,for which appropriate approaches are selected according to the principle of rolling development of unit cells and based on different requirements of different stages.The quick-response and flexible technology system can help the low carbon city to choose an appropriate technology strategy in line with its own characteristics in the start-up stage and rapid development,thus realizing the sustainable leap-forward development and providing reference for other similar regions.

  13. Simultaneous determination of arterial input function of the internal carotid and middle cerebral arteries for dynamic susceptibility contrast MRI

    International Nuclear Information System (INIS)

    Scholdei, R.; Wenz, F.; Fuss, M.; Essig, M.; Knopp, M.V.

    1999-01-01

    Purpose: The determination of the arterial input function (AIF) is necessary for absolute quantification of the regional cerebral blood volume and blood flow using dynamic susceptibility contrast MRI. The suitability of different vessels (ICA-internal carotid artery, MCA-middle cerebral artery) for AIF determination was compared in this study. Methods: A standard 1.5 T MR system and a simultaneous dual FLASH sequence (TR/TE1/TE2/α=32/15/25/10 ) were used to follow a bolus of contrast agent. Slice I was chosen to cut the ICA perpendicularly. Slice II included the MCA. Seventeen data sets from ten subjects were evaluated. Results: The number of AIF-relevant pixels, the area under the AIF and the maximum concentration were all lower when the AIF was determined from the MCA compared to the ICA. Additionally, the mean transit time (MTT) and the time to maximum concentration (TTM) were longer in the MCA, complicating the computerized identification of AIF-relevant pixels. Data from one subject, who was examined five times, demonstrated that the intraindividual variance of the measured parameters was markedly lower than the interpersonal variance. Conclusions: It appears to be advantageous to measure the AIF in the ICA rather than the MCA. (orig.) [de

  14. Observation Platform for Dynamic Biomedical and Biotechnology Experiments Using the International Space Station (ISS) Light Microscopy Module (LMM)

    Science.gov (United States)

    Kurk, Michael A. (Andy)

    2015-01-01

    Techshot, Inc., has developed an observation platform for the LMM on the ISS that will enable biomedical and biotechnology experiments. The LMM Dynamic Stage consists of an electronics module and the first two of a planned suite of experiment modules. Specimens and reagent solutions can be injected into a small, hollow microscope slide-the heart of the innovation-via a combination of small reservoirs, pumps, and valves. A life science experiment module allows investigators to load up to two different fluids for on-orbit, real-time image cytometry. Fluids can be changed to initiate a process, fix biological samples, or retrieve suspended cells. A colloid science experiment module conducts microparticle and nanoparticle tests for investigation of colloid self-assembly phenomena. This module includes a hollow glass slide and heating elements for the creation of a thermal gradient from one end of the slide to the other. The electronics module supports both experiment modules and contains a unique illuminator/condenser for bright and dark field and phase contrast illumination, power supplies for two piezoelectric pumps, and controller boards for pumps and valves. This observation platform safely contains internal fluids and will greatly accelerate the research and development (R&D) cycle of numerous experiments, products, and services aboard the ISS.

  15. Internal tides and sediment dynamics in the deep sea-Evidence from radioactive Th-234/U-238 disequilibria

    International Nuclear Information System (INIS)

    Turnewitsch, R.; Turnewitsch, R.; Waniek, J.J.; Reyss, J.L.; Nycander, J.; Lampitt, R.S.

    2008-01-01

    Residual flow, baro-tropic tides and internal (baro-clinic) tides interact in a number of ways with kilometer-scale sea floor topography such as abyssal hills and sea mounts. Because of their likely impact on vertical mixing such interactions are potentially important for ocean circulation and the mechanisms and the geometry of these interactions are a matter of ongoing studies. In addition, very little is known about how these interactions are reflected in the sedimentary record. This multi-year study investigates if flow/topography interactions are reflected in distributional patterns of the natural short-lived (half-life: 24.1 d) particulate-matter tracer 234 Th relative to its conservative (non-particle-reactive) and very long-lived parent nuclide 238 U. The sampling sites were downstream of, or surrounded by, fields of short sea mounts and, therefore, very likely to be influenced by nearby flow/topography interactions. At the sampling sites between about 200 and 1000 m above the sea floor recurrent 'fossil' disequilibria were detected. 'Fossil' disequilibria are defined by clearly detectable 234 Th/ 238 U disequilibria (total 234 Th radioactivity ≤ 238 U radioactivity, indicating a history of intense particulate 234 Th scavenging and particulate-matter settling from the sampled parcel of water) and conspicuously low particle-associated 234 Th activities. 'Fossil' disequilibria were centered at levels in the water column that correspond to the average height of the short sea mounts near the sampling sites. This suggests the 'fossil' disequilibria are formed on the sea mount slopes. Moreover, the magnitude of the 'fossil' disequilibria suggests that the slopes of the short sea mounts in the study region are characterized by particularly vigorous fluid dynamics. Since 'fossil' disequilibria already occurred at ∼ O (1-10 km) away from the sea mount slopes it is likely that these vigorous fluid dynamics rapidly decay away from the slopes on scales of O (1-10 km

  16. An under-active or over-active internal world? An exploration of parallel dynamics within psyche and soma, and the difficulty of internal regulation, in patients with Chronic Fatigue Syndrome and Myalgic Encephalomyelitis.

    Science.gov (United States)

    Driver, Christine

    2005-04-01

    This paper explores the dynamics brought into analytic work when there is a symmetric fusion between psyche and soma within the patient. It will consider how such a fusion may emerge from reverberations between physical constitution and a lack of maternal attunement, containment and reflective function. I will describe the work with a patient, Jane, who was diagnosed with Myalgic Encephalomyelitis (ME) during the course of her analysis. The dynamic of her physical symptoms within the analytic work, and the impact of her internal affects and internal 'objects' within the transference and countertransference, indicated a difficulty in finding an homeostatic balance resulting in overactivity and underactivity at both somatic and psychological levels. Using the clinical work with Jane this paper will also examine the interrelationship between mother-infant attachment, an inadequate internalized maternal reflective function, affect dysregulation, unconscious fusion, the lack of psyche-soma differentiation and the impact of the latter in relation to internal regulation systems, or lack of, in patients with Chronic Fatigue Syndrome (CFS) and Myalgic Encephalomyelitis (ME). I will draw on similar work carried out by Holland (1997), Simpson (1997) and Simpson et al. (1997). The paper will also employ the concept of the reflective function (Fonagy 2001; Knox 2003), and consider Matte-Blanco's (1999) concepts of generalization and unconscious symmetry in relation to the patient's internal world. I go on to consider how analysis provides a point outside the 'fusion' that can enable the 'deadlock' to be broken.

  17. Protein Internal Dynamics Associated With Pre-System Glass Transition Temperature Endothermic Events: Investigation of Insulin and Human Growth Hormone by Solid State Hydrogen/Deuterium Exchange.

    Science.gov (United States)

    Fang, Rui; Grobelny, Pawel J; Bogner, Robin H; Pikal, Michael J

    2016-11-01

    Lyophilized proteins are generally stored below their glass transition temperature (T g ) to maintain long-term stability. Some proteins in the (pure) solid state showed a distinct endotherm at a temperature well below the glass transition, designated as a pre-T g endotherm. The pre-T g endothermic event has been linked with a transition in protein internal mobility. The aim of this study was to investigate the internal dynamics of 2 proteins, insulin and human growth hormone (hGH), both of which exhibit the pre-T g endothermic event with onsets at 50°C-60°C. Solid state hydrogen/deuterium (H/D) exchange of both proteins was characterized by Fourier transform infrared spectroscopy over a temperature range from 30°C to 80°C. A distinct sigmoidal transition in the extent of H/D exchange had a midpoint of 56.1 ± 1.2°C for insulin and 61.7 ± 0.9°C for hGH, suggesting a transition to greater mobility in the protein molecules at these temperatures. The data support the hypothesis that the pre-T g event is related to a transition in internal protein mobility associated with the protein dynamical temperature. Exceeding the protein dynamical temperature is expected to activate protein internal motion and therefore may have stability consequences. Copyright © 2016 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

  18. The internal model: A study of the relative contribution of proprioception and visual information to failure detection in dynamic systems. [sensitivity of operators versus monitors to failures

    Science.gov (United States)

    Kessel, C.; Wickens, C. D.

    1978-01-01

    The development of the internal model as it pertains to the detection of step changes in the order of control dynamics is investigated for two modes of participation: whether the subjects are actively controlling those dynamics or are monitoring an autopilot controlling them. A transfer of training design was used to evaluate the relative contribution of proprioception and visual information to the overall accuracy of the internal model. Sixteen subjects either tracked or monitored the system dynamics as a 2-dimensional pursuit display under single task conditions and concurrently with a sub-critical tracking task at two difficulty levels. Detection performance was faster and more accurate in the manual as opposed to the autopilot mode. The concurrent tracking task produced a decrement in detection performance for all conditions though this was more marked for the manual mode. The development of an internal model in the manual mode transferred positively to the automatic mode producing enhanced detection performance. There was no transfer from the internal model developed in the automatic mode to the manual mode.

  19. Conformation and dynamics of nucleotides in bulges and symmetric internal loops in duplex DNA studied by EPR and fluorescence spectroscopies

    International Nuclear Information System (INIS)

    Cekan, Pavol; Sigurdsson, Snorri Th.

    2012-01-01

    Highlights: ► Bulges and loops were studied by both EPR and fluorescence spectroscopies using the probe Ç/Ç f . ► One-base bulge was in a temperature-dependent equilibrium between looped-out and stacked states. ► Bases in two- and three-base bulges were stacked at all temperatures, resulting in DNA bending. ► Bases were stacked in symmetrical two- to five-base internal loops, according to EPR data. ► Unexpectedly high fluorescence for the smaller loops indicated local structural perturbations. -- Abstract: The dynamics and conformation of base bulges and internal loops in duplex DNA were studied using the bifunctional spectroscopic probe Ç, which becomes fluorescent (Ç f ) upon reduction of the nitroxide functional group, along with EPR and fluorescence spectroscopies. A one-base bulge was in a conformational equilibrium between looped-out and stacked states, the former favored at higher temperature and the latter at lower temperature. Stacking of bulge bases was favored in two- and three-base bulges, independent of temperature, resulting in DNA bending as evidenced by increased fluorescence of Ç f . EPR spectra of Ç-labeled three-, four- and five-base symmetrical interior DNA bulges at 20 °C showed low mobility, indicating that the spin-label was stacked within the loop. The spin-label mobility at 37 °C increased as the loops became larger. A considerable variation in fluorescence between different loops was observed, as well as a temperature-dependence within constructs. Fluorescence unexpectedly increased as the size of the loop decreased at 2 °C. Fluorescence of the smallest loops, where a single T·T mismatch was located between the stem region and the probe, was even larger than for the single strand, indicating a considerable local structural deformation of these loops from regular B-DNA. These results show the value of combining EPR and fluorescence spectroscopy to study non-helical regions of nucleic acids.

  20. Diazo Esters as Dienophiles in Intramolecular (4 + 2) Cycloadditions: Computational Explorations of Mechanism.

    Science.gov (United States)

    Duan, Abing; Yu, Peiyuan; Liu, Fang; Qiu, Huang; Gu, Feng Long; Doyle, Michael P; Houk, K N

    2017-02-22

    The first experimental examples of Diels-Alder (DA) reactions of diazo compounds as heterodienophiles with dienes have been studied with density functional theory (DFT) using the M06-2X functional. For comparison, the reactivities of diazo esters as dienophiles or 1,3-dipoles with 1,3-dienes in intermolecular model systems have been analyzed by the distortion/interaction model. The 1,3-dipolar cycloaddition is strongly favored for the intermolecular system. The intramolecular example is unique because the tether strongly favors the (4 + 2) cycloaddition.

  1. Enantioselective Intramolecular CH-Insertions upon Cu-Catalyzed Decomposition of Phenyliodonium Ylides

    Directory of Open Access Journals (Sweden)

    Christelle Boléa

    2001-02-01

    Full Text Available The Cu-catalyzed intramolecular CH insertion of phenyliodonium ylide 5b has been investigated at 0° C in the presence of several chiral ligands. Enantioselectivities vary in the range of 38–72 %, and are higher than those resulting from reaction of the diazo compound 5c at 65° C. The results are consistent with a carbenoid mechanism for Cu-catalyzed decomposition of phenyliodonium ylides.

  2. Fused-Ring Formation by an Intramolecular "Cut-and-Sew" Reaction between Cyclobutanones and Alkynes.

    Science.gov (United States)

    Deng, Lin; Jin, Likun; Dong, Guangbin

    2018-03-01

    The development of a catalytic intramolecular "cut-and-sew" transformation between cyclobutanones and alkynes to construct cyclohexenone-fused rings is described herein. The challenge arises from the need for selective coupling at the more sterically hindered proximal position, and can be addressed by using an electron-rich, but less bulky, phosphine ligand. The control experiment and 13 C-labelling study suggest that the reaction may start with cleavage of the less hindered distal C-C bond of cyclobutanones, followed by decarbonylation and CO reinsertion to enable Rh insertion at the more hindered proximal position. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Intramolecular transformation of thiyl radicals to α-aminoalkyl radicals: 'ab initio' calculations on homocystein

    International Nuclear Information System (INIS)

    Chhun, S.; Berges, J.; Bleton, V.; Abedinzadeh, Z.

    2000-01-01

    One-electron oxidation of thiols by oxidizing radicals leads to the formation of thiyl radical and carbon-centered radicals. It has been shown experimentally that in the absence of oxygen, the thiyl radicals derived from certain thiols of biological interest such as glutathion, cysteine and homocysteine decay rapidly by intramolecular rearrangement reactions into the carbon-centered radical. In the present work we have investigated theoretically the structure and the stability of thiyl and carbon-centered radicals of homocysteine in order to check the possibility of this rearrangement. (author)

  4. Specific optical signalling of anions via intramolecular charge transfer pathway based on acridinedione fluorophore

    International Nuclear Information System (INIS)

    Thiagarajan, Viruthachalam; Ramamurthy, Perumal

    2007-01-01

    We present a simple but highly specific acridinedione fluorophore (ADD-1) that acts both as a fluorescent and colorimetric sensor for anions in acetonitrile. The specific optical signalling of ADD-1 is due to the formation of new distinct intramolecular charge transfer (ICT) emitting states in the presence of AcO - (490 nm), H 2 PO 4 - (440 nm), and F - (510 nm) over other anions. Presence of F - shows a colour change that is perceptible to the naked eye, from colourless to an intense fluorescent green due to the deprotonation of acridinedione ring amino hydrogen

  5. The preparation and intramolecular radical cyclisation reactions of chiral oxyme ethers

    International Nuclear Information System (INIS)

    Booth, Susan E.; Jenkins, Paul R.

    1998-01-01

    Chiral oxime ether 2 and Oxime ester 4 have been prepared by alkylation and esterification of the oxime 1. Racemic hydroxylamine 6 and chiral hydroxylamine 10 have been synthesised from N-hydroxysuccinimide and the corresponding alcohol in the presence of diethyl azo dicarboxylate, the two product were converted into the oxime ethers 7 and 11 respectively. The intramolecular radical cyclisation reactions of these oxime ethers and esters has been studied, successful reaction was observed to produce alkyl hydroxylamines 3,8 and 12. (author)

  6. The Preparation and Intramolecular Radical Cyclisation Reactions of Chiral Oxime Ethers

    Directory of Open Access Journals (Sweden)

    Booth Susan E.

    1998-01-01

    Full Text Available Chiral oxime ether 2 and Oxime ester 4 have been prepared by alkylation and esterification of the oxime 1. Racemic hydroxylamine 6 and chiral hydroxylamine 10 have been synthesised from N-hydroxysuccinimide and the corresponding alcohol in the presence of diethylazodicarboxylate, the two products were converted into the oxime ethers 7 and 11 respectively. The intramolecular radical cyclisation reactions of these oxime ethers and esters has been studied, successful reaction was observed to produce alkyl hydroxylamines 3, 8 and 12.

  7. Synthesis and Intramolecular [4+2] Cycloaddition Reactions of 4-Pyridazinecarbonitriles with Alkyne Side Chains

    Directory of Open Access Journals (Sweden)

    Norbert Haider

    1998-01-01

    Full Text Available The preparation of a series of new 3-(alkynyl-X-substituted 4-pyridazinecarbonitriles 2-5 (X = O, NH is described. The compounds are shown to undergo thermally induced intramolecular Diels-Alder reactions with inverse electron demand, affording the fused benzonitriles 6-8. Incorporation of a 1,2-phenylene unit into the side chain, as in the case of compounds 10 and 13, results in a more favorable conformation of the dienophilic substructure and thus to a pronounced acceleration of the [4+2] cycloaddition reaction.

  8. Influence of intramolecular hydrogen bonds on the binding potential of methylated β-cyclodextrin derivatives

    Directory of Open Access Journals (Sweden)

    Gerhard Wenz

    2012-11-01

    Full Text Available Various heptasubstituted derivatives of β-cyclodextrin (β-CD bearing 1, 2 and 3 methyl substituents per glucose unit were synthesized by regioselective methods. Binding free energies and binding enthalpies of these hosts towards 4-tert-butylbenzoate and adamantane-1-carboxylate were determined by isothermal titration microcalorimetry (ITC. It was found that methyl substituents at the secondary positions of β-CD lead to a tremendous reduction of the binding potential, while methylation at the primary positions significantly improved binding. Stabilizing intramolecular hydrogen bonds between the glucose units were made responsible for the high binding potentials of those β-CD derivatives that possess secondary hydroxy groups.

  9. Deuterium isotope effect on the intramolecular electron transfer in Pseudomonas aeruginosa azurin

    DEFF Research Database (Denmark)

    Farver, O.; Zhang, Jingdong; Chi, Qijin

    2001-01-01

    rather than negative. Isotope effects are, however, also inherent in the nuclear reorganization Gibbs free energy and in the tunneling factor for the electron transfer process. A slightly larger thermal protein expansion in H2O than in D2O (0.001 nm K-1) is sufficient both to account for the activation......Intramolecular electron transfer in azurin in water and deuterium oxide has been studied over a broad temperature range. The kinetic deuterium isotope effect, k(H)/k(D), is smaller than unity (0.7 at 298 K), primarily caused by the different activation entropies in water (-56.5 J K-1 mol(-1...

  10. Use of ionic model for analysis of intramolecular movement in alkali metal metaborate molecules

    International Nuclear Information System (INIS)

    Ezhov, Yu.S.; Vinogradov, V.S.

    1978-01-01

    To clear out the peculiarities of intramolecular movement in MBO 2 (where M=Li, Na, K, Rb, Cs) molecules the energy dependence of cation electrostatic interaction with BO 2 anion on the charge value of oxygen, values of the MOB valence angle and internuclear distance r(M-O) is calculated. The calculation results on the base of ionic model show that the minimum of potential energy function corresponds to angular configuration of the MBO 2 molecules. Parameters of potential function of deformation oscillation connected with the change of MOB angle, are evaluated

  11. Cooperative Metal–Ligand Catalyzed Intramolecular Hydroamination and Hydroalkoxylation of Allenes Using a Stable Iron Catalyst

    KAUST Repository

    El-Sepelgy, Osama

    2018-01-18

    A new iron-catalyzed chemoselective intramolecular hydroamination and hydroalkoxylation of the readily available α-allenic amines and alcohols to valuable unsaturated 5-membered heterocycles, 2,3-dihydropyrrole and 2,3-dihydrofuran, is reported. Effective selectivity control is achieved by a metal–ligand cooperative activation of the substrates. The mild reaction conditions and the use of low amounts of an air and moisture stable iron catalyst allow for the hydrofunctionalization of a wide range of allenes bearing different functional groups in good yields in the absence of base or any sensitive additives.

  12. A concise, efficient synthesis of sugar-based benzothiazoles through chemoselective intramolecular C-S coupling

    KAUST Repository

    Shen, Chao

    2012-01-01

    Sugar-based benzothiazoles are a new class of molecules promising for many biological applications. Here, we have synthesized a wide range of sugar-based benzothiazoles from readily accessible glycosyl thioureas by chemoselective, palladium-catalyzed C-S coupling reactions. Corroborated by theoretical calculations, a mechanistic investigation indicates that the coordination to the palladium by a pivaloyl carbonyl group and the presence of intramolecular hydrogen bonding play important roles in the efficiency and chemoselectivity of reaction. These fluorescent glycoconjugates can be observed to readily enter mammalian tumor cells and exhibit potential in vitro antitumor activity. This journal is © The Royal Society of Chemistry 2012.

  13. Cooperative Metal–Ligand Catalyzed Intramolecular Hydroamination and Hydroalkoxylation of Allenes Using a Stable Iron Catalyst

    KAUST Repository

    El-Sepelgy, Osama; Brzozowska, Aleksandra; Sklyaruk, Jan; Jang, Yoon Kyung; Zubar, Viktoriia; Rueping, Magnus

    2018-01-01

    A new iron-catalyzed chemoselective intramolecular hydroamination and hydroalkoxylation of the readily available α-allenic amines and alcohols to valuable unsaturated 5-membered heterocycles, 2,3-dihydropyrrole and 2,3-dihydrofuran, is reported. Effective selectivity control is achieved by a metal–ligand cooperative activation of the substrates. The mild reaction conditions and the use of low amounts of an air and moisture stable iron catalyst allow for the hydrofunctionalization of a wide range of allenes bearing different functional groups in good yields in the absence of base or any sensitive additives.

  14. Pulse radiolytic and electrochemical investigations of intramolecular electron transfer in carotenoporphyrins and carotenoporphyrin-quinone triads

    International Nuclear Information System (INIS)

    Land, E.J.; Lexa, D.; Bensasson, R.V.; Gust, D.; Moore, T.A.; Moore, A.L.; Liddell, P.A.; Nemeth, G.A.

    1987-01-01

    Thermodynamic and kinetic aspects of intramolecular electron-transfer reactions in carotenoporphyrin dyads and carotenoid-porphyrin-quinone triads have been studied by using pulse radiolysis and cyclic voltammetry. Rapid (<1 μs) electron transfer from carotenoid radical anions to attached porphyrins has been inferred. Carotenoid cations, on the other hand, do not readily accept electrons from attached porphyrins or pyropheophorbides. Electrochemical studies provide the thermodynamic basis for these observations and also allow estimation of the energetics of photoinitiated two-step electron transfer and two-step charge recombination in triad models for photosynthetic charge separation

  15. DYNAMICS OF HIGHGER MENTAL FUNCTION IN PATIENTS WITH OBLITERATING LESIONS OF INTERNAL CAROTID ARTERIES IN SURGICAL BRAIN REVASCUL

    Directory of Open Access Journals (Sweden)

    R. A. Vinogradov

    2017-01-01

    Full Text Available Obliterating atherosclerosis of internal carotid arteries is one of the main causes of ischemic stroke and discirculatory encephalopathy. It causes up to 40% of ischemic disorders of cerebral circulation. Currently, the strategy for stroke prevention is determined by the intensive development of surgical methods of treatment, primarily methods for managing lesions of brachiocephalic arteries. Based on the results of a number of international multicenter randomized studies, indications for reconstructive operations for BCA, tactics for managing patients in the postoperative period were formulated. A number of patients with atherosclerotic lesions of brachiocephalic arteries have reduced cognitive functions. The aim of the study is to compare cognitive functions (CF in patients who underwent different surgical approaches in the treatment of obliterating atherosclerotic lesion of internal carotid arteries (ICA.MATERIAL AND METHODS. We studied higher mental functions (HMFs in 116 patients with obliterating unilateral or bilateral lesion of ICA. The study of cognitive functions (MF was performed prior to carotid endarterectomy (CE, group 1, n=73 and transluminal balloon angioplasty of ICAs (TBA of ICA, group 2, n=43, and on days 5–7 and 30–31 after cerebral revascularization (CR. To assess the overall severity of cognitive impairment, the summary indicators of main screening neuropsychological tests were used: MMSE; MoCA; Frontal Assessment Battery (FAB; Beck Depression Inventory and Hamilton Depression Rating Scale.RESULTS. Results Neuropsychologic disorders were reavealed in 98% of patients prior to surgery. An initially comparable condition of HMF in groups with CE and TBA of ICA was revealed. MMSE2 revealed a significant improvement in the results in group 1 both in comparison with the initial data (p<0.05 and in comparison with the results of the second test of group 2. The results of MMSE1 and MMSE2 in group 2 did not show significant

  16. Histone H1 chaperone activity of TAF-I is regulated by its subtype-dependent intramolecular interaction.

    Science.gov (United States)

    Kajitani, Kaori; Kato, Kohsuke; Nagata, Kyosuke

    2017-04-01

    Linker histone H1 is involved in the regulation of gene activity through the maintenance of higher-order chromatin structure. Previously, we have shown that template activating factor-I (TAF-I or protein SET) is involved in linker histone H1 dynamics as a histone H1 chaperone. In human and murine cells, two TAF-I subtypes exist, namely TAF-Iα and TAF-Iβ. TAF-I has a highly acidic amino acid cluster in its C-terminal region and forms homo- or heterodimers through its dimerization domain. Both dimer formation and the C-terminal region of TAF-I are essential for the histone chaperone activity. TAF-Iα exhibits less histone chaperone activity compared with TAF-Iβ even though TAF-Iα and β differ only in their N-terminal regions. However, it is unclear how subtype-specific TAF-I activities are regulated. Here, we have shown that the N-terminal region of TAF-Iα autoinhibits its histone chaperone activity via intramolecular interaction with its C-terminal region. When the interaction between the N- and C-terminal regions of TAF-Iα is disrupted, TAF-Iα shows a histone chaperone activity similar to that of TAF-Iβ. Taken together, these results provide mechanistic insights into the concept that fine tuning of TAF-I histone H1 chaperone activity relies on the subtype compositions of the TAF-I dimer. © 2017 Molecular Biology Society of Japan and John Wiley & Sons Australia, Ltd.

  17. Modeling the Alzheimer Abeta17-42 fibril architecture: tight intermolecular sheet-sheet association and intramolecular hydrated cavities.

    Science.gov (United States)

    Zheng, Jie; Jang, Hyunbum; Ma, Buyong; Tsai, Chung-Jun; Nussinov, Ruth

    2007-11-01

    We investigate Abeta(17-42) protofibril structures in solution using molecular dynamics simulations. Recently, NMR and computations modeled the Abeta protofibril as a longitudinal stack of U-shaped molecules, creating an in-parallel beta-sheet and loop spine. Here we study the molecular architecture of the fibril formed by spine-spine association. We model in-register intermolecular beta-sheet-beta-sheet associations and study the consequences of Alzheimer's mutations (E22G, E22Q, E22K, and M35A) on the organization. We assess the structural stability and association force of Abeta oligomers with different sheet-sheet interfaces. Double-layered oligomers associating through the C-terminal-C-terminal interface are energetically more favorable than those with the N-terminal-N-terminal interface, although both interfaces exhibit high structural stability. The C-terminal-C-terminal interface is essentially stabilized by hydrophobic and van der Waals (shape complementarity via M35-M35 contacts) intermolecular interactions, whereas the N-terminal-N-terminal interface is stabilized by hydrophobic and electrostatic interactions. Hence, shape complementarity, or the "steric zipper" motif plays an important role in amyloid formation. On the other hand, the intramolecular Abeta beta-strand-loop-beta-strand U-shaped motif creates a hydrophobic cavity with a diameter of 6-7 A, allowing water molecules and ions to conduct through. The hydrated hydrophobic cavities may allow optimization of the sheet association and constitute a typical feature of fibrils, in addition to the tight sheet-sheet association. Thus, we propose that Abeta fiber architecture consists of alternating layers of tight packing and hydrated cavities running along the fibrillar axis, which might be possibly detected by high-resolution imaging.

  18. On the intramolecular proton transfer of 3-hydroxyflavone in the first singlet excited state: A theoretical study

    International Nuclear Information System (INIS)

    Casadesus, Ricard; Vendrell, Oriol; Moreno, Miquel; Lluch, Jose M.; Morokuma, Keiji

    2006-01-01

    The intramolecular proton-transfer reaction in 3-hydroxyflavone (3HF) is theoretically studied both in the ground (S 0 ) and first singlet excited (S 1 ) electronic states. In S 0 the proton-transfer reaction is shown to be quite unfavorable at the DFT (B3LYP) level. However, the back proton transfer is found to be a feasible process with a small energy barrier, both results being in qualitative agreement with known experimental facts. Different theoretical levels are considered and compared for S 1 . The ab initio configuration interaction singles (CIS) method overestimates the energy of S 1 and give too high energy barriers for the proton-transfer reaction. The complete active space SCF (CASSCF) method gives a more reasonable value but the inclusion of the dynamical correlation through second-order perturbation theory (CASPT2) upon CASSCF geometries or the use of the time-dependent DFT (TDDFT) method upon CIS geometries gives a barrierless process. Optimization of geometries (minima and transition-state structures) at the TDDFT level leads to a small but non-negligible energy barrier for the proton-transfer reaction in S 1 and global energies that fit quite well with the known experimental (spectroscopic and femtochemistry) data. Finally the effect of a polar environment is analyzed through a continuum model, which gives only a small difference from the previous gas-phase results. This points out that the remarkable changes in the photochemistry of 3HF observed experimentally are not to be solely attributed to the polarity of the surrounding media

  19. On the intramolecular proton transfer of 3-hydroxyflavone in the first singlet excited state: A theoretical study

    Energy Technology Data Exchange (ETDEWEB)

    Casadesus, Ricard [Departament de Quimica, Universitat Autonoma de Barcelona, 08193 Bellaterra, Barcelona (Spain); Cherry L. Emerson Center for Scientific Computation and Department of Chemistry, Emory University, Atlanta, GA 30322 (United States); Vendrell, Oriol [Departament de Quimica, Universitat Autonoma de Barcelona, 08193 Bellaterra, Barcelona (Spain); Moreno, Miquel [Departament de Quimica, Universitat Autonoma de Barcelona, 08193 Bellaterra, Barcelona (Spain)], E-mail: mmf@klingon.uab.es; Lluch, Jose M. [Departament de Quimica, Universitat Autonoma de Barcelona, 08193 Bellaterra, Barcelona (Spain); Morokuma, Keiji [Cherry L. Emerson Center for Scientific Computation and Department of Chemistry, Emory University, Atlanta, GA 30322 (United States)

    2006-06-20

    The intramolecular proton-transfer reaction in 3-hydroxyflavone (3HF) is theoretically studied both in the ground (S{sub 0}) and first singlet excited (S{sub 1}) electronic states. In S{sub 0} the proton-transfer reaction is shown to be quite unfavorable at the DFT (B3LYP) level. However, the back proton transfer is found to be a feasible process with a small energy barrier, both results being in qualitative agreement with known experimental facts. Different theoretical levels are considered and compared for S{sub 1}. The ab initio configuration interaction singles (CIS) method overestimates the energy of S{sub 1} and give too high energy barriers for the proton-transfer reaction. The complete active space SCF (CASSCF) method gives a more reasonable value but the inclusion of the dynamical correlation through second-order perturbation theory (CASPT2) upon CASSCF geometries or the use of the time-dependent DFT (TDDFT) method upon CIS geometries gives a barrierless process. Optimization of geometries (minima and transition-state structures) at the TDDFT level leads to a small but non-negligible energy barrier for the proton-transfer reaction in S{sub 1} and global energies that fit quite well with the known experimental (spectroscopic and femtochemistry) data. Finally the effect of a polar environment is analyzed through a continuum model, which gives only a small difference from the previous gas-phase results. This points out that the remarkable changes in the photochemistry of 3HF observed experimentally are not to be solely attributed to the polarity of the surrounding media.

  20. The disordered C-terminal domain of human DNA glycosylase NEIL1 contributes to its stability via intramolecular interactions.

    Science.gov (United States)

    Hegde, Muralidhar L; Tsutakawa, Susan E; Hegde, Pavana M; Holthauzen, Luis Marcelo F; Li, Jing; Oezguen, Numan; Hilser, Vincent J; Tainer, John A; Mitra, Sankar

    2013-07-10

    NEIL1 [Nei (endonuclease VIII)-like protein 1], one of the five mammalian DNA glycosylases that excise oxidized DNA base lesions in the human genome to initiate base excision repair, contains an intrinsically disordered C-terminal domain (CTD; ~100 residues), not conserved in its Escherichia coli prototype Nei. Although dispensable for NEIL1's lesion excision and AP lyase activities, this segment is required for efficient in vivo enzymatic activity and may provide an interaction interface for many of NEIL1's interactions with other base excision repair proteins. Here, we show that the CTD interacts with the folded domain in native NEIL1 containing 389 residues. The CTD is poised for local folding in an ordered structure that is induced in the purified fragment by osmolytes. Furthermore, deletion of the disordered tail lacking both Tyr and Trp residues causes a red shift in NEIL1's intrinsic Trp-specific fluorescence, indicating a more solvent-exposed environment for the Trp residues in the truncated protein, which also exhibits reduced stability compared to the native enzyme. These observations are consistent with stabilization of the native NEIL1 structure via intramolecular, mostly electrostatic, interactions that were disrupted by mutating a positively charged (Lys-rich) cluster of residues (amino acids 355-360) near the C-terminus. Small-angle X-ray scattering (SAXS) analysis confirms the flexibility and dynamic nature of NEIL1's CTD, a feature that may be critical to providing specificity for NEIL1's multiple, functional interactions. Copyright © 2013 Elsevier Ltd. All rights reserved.

  1. The role of intramolecular crosslinking in the radiolysis of bulk crystallized high density polyethylene

    International Nuclear Information System (INIS)

    Lyons, B.J.

    1986-01-01

    Intramolecular crosslinks have been suggested to occur in bulk crystallized, irradiated, high density polyethylene (HDPE) and to account for the low rates of gel formation, especially those of previously annealed samples when compared with that manifested by the same resin when previously quenched from the melt. Such crosslinks do not contribute to the development of gel and contribute to only a limited extent to the elastic properties above the crystalline melting point when compared with intermolecular crosslinks, but, if the mesh size of the intra- and inter-molecular networks are comparable, are fully reflected in the rupture elongation. The rupture elongations of a wide range of HDPE resins, for a given sol fraction or elastic modulus, are found to be at least as high as and often higher than those of low (LDPE) or linear low (LLDPE) polyethylene resins, indicating that intramolecular crosslinking of this type does not occur to a significantly greater extent in these higher crystallinity resins. Other factors more likely to account for the reduced rates of inter alia gel formation in some HDPE resins are discussed. (author)

  2. EVAPORATION: a new vapour pressure estimation methodfor organic molecules including non-additivity and intramolecular interactions

    Directory of Open Access Journals (Sweden)

    S. Compernolle

    2011-09-01

    Full Text Available We present EVAPORATION (Estimation of VApour Pressure of ORganics, Accounting for Temperature, Intramolecular, and Non-additivity effects, a method to predict (subcooled liquid pure compound vapour pressure p0 of organic molecules that requires only molecular structure as input. The method is applicable to zero-, mono- and polyfunctional molecules. A simple formula to describe log10p0(T is employed, that takes into account both a wide temperature dependence and the non-additivity of functional groups. In order to match the recent data on functionalised diacids an empirical modification to the method was introduced. Contributions due to carbon skeleton, functional groups, and intramolecular interaction between groups are included. Molecules typically originating from oxidation of biogenic molecules are within the scope of this method: aldehydes, ketones, alcohols, ethers, esters, nitrates, acids, peroxides, hydroperoxides, peroxy acyl nitrates and peracids. Therefore the method is especially suited to describe compounds forming secondary organic aerosol (SOA.

  3. [Development of boomerang-type intramolecular cascade reactions and application to natural product synthesis].

    Science.gov (United States)

    Takasu, K

    2001-12-01

    Intramolecular cascade reaction has received much attention as a powerful methodology to construct a polycyclic framework in organic synthesis. We have been developing "boomerang-type cascade reaction" to construct a variety of polycyclic skeletons efficiently. In the above reactions, a nucleophilic function of substrates changes the character into an electrophile after the initial reaction, and the electrophilic group acts as a nucleophile in the second reaction. That is, the reaction center stepwise moves from one functional group back to the same one via other functional groups. The stream of the electron concerning the cascade reaction is like a locus of boomerang. We show here three different boomerang-type reactions via ionic species or free radicals. 1) Diastereoselective Michael-aldol reaction based on the chiral auxiliary method and enantioselective Michael-aldol reaction by the use of external chiral sources. 2) Short and efficient total syntheses of longifolane sesquiterpenes utilizing intramolecular double Michael addition as a key step. 3) Development of boomerang-type radical cascade reaction of halopolyenes to construct terpenoid skeletons and its regioselectivity.

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

    KAUST Repository

    Poater, Albert

    2013-03-15

    The present paper gives insight into an intramolecular dechlorination reaction involving Copper (I) and an ArCH2Cl moiety. The discussion of the presence of a CuIII organometallic intermediate becomes a challenge, and because of the lack of clear experimental detection of this proposed intermediate, and due to the computational evidence that it is less stable than other isomeric species, it can be ruled out for the complex studied here. Our calculations are completely consistent with the key hypothesis of Karlin et al. that TMPA-CuI is the substrate of intramolecular dechlorination reactions as well as the source to generate organometallic species. However the organometallic character of some intermediates has been refused because computationally these species are less stable than other isomers. Thus this study constitutes an additional piece towards the full understanding of a class of reaction of biological relevance. Further, the lack of high energy barriers and deep energy wells along the reaction pathway explains the experimental difficulties to trap other intermediates. © Springer-Verlag Berlin Heidelberg 2013.

  5. An excited-state intramolecular photon transfer fluorescence probe for localizable live cell imaging of cysteine

    Science.gov (United States)

    Liu, Wei; Chen, Wen; Liu, Si-Jia; Jiang, Jian-Hui

    2017-03-01

    Small molecule probes suitable for selective and specific fluorescence imaging of some important but low-concentration intracellular reactive sulfur species such as cysteine (Cys) pose a challenge in chemical biology. We present a readily available, fast-response fluorescence probe CHCQ-Ac, with 2-(5‧-chloro-2-hydroxyl-phenyl)-6-chloro-4(3 H)-quinazolinone (CHCQ) as the fluorophore and acrylate group as the functional moiety, that enables high-selectivity and high-sensitivity for detecting Cys in both solution and biological system. After specifically reacted with Cys, the probe undergoes a seven-membered intramolecular cyclization and released the fluorophore CHCQ with excited-state intramolecular photon transfer effect. A highly fluorescent, insoluble aggregate was then formed to facilitate high-sensitivity and high-resolution imaging. The results showed that probe CHCQ-Ac affords a remarkably large Stokes shift and can detect Cys under physiological pH condition with no interference from other analytes. Moreover, this probe was proved to have excellent chemical stability, low cytotoxicity and good cell permeability. Our design of this probe provides a novel potential tool to visualize and localize cysteine in bioimaging of live cells that would greatly help to explore various Cys-related physiological and pathological cellular processes in cell biology and diagnostics.

  6. Structural, photophysical, and theoretical studies of imidazole-based excited-state intramolecular proton transfer molecules

    Science.gov (United States)

    Somasundaram, Sivaraman; Kamaraj, Eswaran; Hwang, Su Jin; Park, Sanghyuk

    2018-02-01

    Imidazole-based excited state intramolecular proton transfer (ESIPT) blue fluorescent molecules, 2-(1-(4-chlorophenyl)-4,5-diphenyl-1H-imidazol-2-yl)phenol (BHPI-Cl) and 2-(1-(4-bromophenyl)-4,5-diphenyl-1H-imidazol-2-yl)phenol (BHPI-Br) were designed and synthesized by Debus-Radziszewski method through a one-pot multicomponent reaction in high yield. The synthesized compounds were fully characterized by 1H NMR, 13C NMR, FT-IR, FT-Raman, GC-Mass, and elemental analysis. The molecular structures in single crystal lattice were studied by X-ray crystallographic analysis. Because of the intramolecular hydrogen bonding, hydroxyphenyl group is planar to the central imidazole ring, while the other phenyl rings gave distorted conformations to the central heterocyclic ring. BHPI-Cl and BHPI-Br molecules showed intense ESIPT fluorescence at 480 nm, because the two twisted phenyl rings on 4- and 5-positions have reduced intermolecular interaction between adjacent molecules in each crystal through a head-to-tail packing manner. Quantum chemical calculations of energies were carried out by (TD-)DFT using B3LYP/6-31G(d, p) basis set to predict the electronic absorption spectra of the compounds, and they showed good agreement between the computational and the experimental values. The thermal analyses of the synthesized molecules were also carried out by TGA/DSC method.

  7. Flow Cytometry Enables Multiplexed Measurements of Genetically Encoded Intramolecular FRET Sensors Suitable for Screening.

    Science.gov (United States)

    Doucette, Jaimee; Zhao, Ziyan; Geyer, Rory J; Barra, Melanie M; Balunas, Marcy J; Zweifach, Adam

    2016-07-01

    Genetically encoded sensors based on intramolecular FRET between CFP and YFP are used extensively in cell biology research. Flow cytometry has been shown to offer a means to measure CFP-YFP FRET; we suspected it would provide a unique way to conduct multiplexed measurements from cells expressing different FRET sensors, which is difficult to do with microscopy, and that this could be used for screening. We confirmed that flow cytometry accurately measures FRET signals using cells transiently transfected with an ERK activity reporter, comparing responses measured with imaging and cytometry. We created polyclonal long-term transfectant lines, each expressing a different intramolecular FRET sensor, and devised a way to bar-code four distinct populations of cells. We demonstrated the feasibility of multiplexed measurements and determined that robust multiplexed measurements can be conducted in plate format. To validate the suitability of the method for screening, we measured responses from a plate of bacterial extracts that in unrelated experiments we had determined contained the protein kinase C (PKC)-activating compound teleocidin A-1. The multiplexed assay correctly identifying the teleocidin A-1-containing well. We propose that multiplexed cytometric FRET measurements will be useful for analyzing cellular function and for screening compound collections. © 2016 Society for Laboratory Automation and Screening.

  8. Effect of Hartree-Fock exact exchange on intramolecular magnetic coupling constants of organic diradicals

    Science.gov (United States)

    Cho, Daeheum; Ko, Kyoung Chul; Ikabata, Yasuhiro; Wakayama, Kazufumi; Yoshikawa, Takeshi; Nakai, Hiromi; Lee, Jin Yong

    2015-01-01

    The intramolecular magnetic coupling constant (J) of diradical systems linked with five- or six-membered aromatic rings was calculated to obtain the scaling factor (experimental J/calculated J ratio) for various density functional theory (DFT) functionals. Scaling factors of group A (PBE, TPSSh, B3LYP, B97-1, X3LYP, PBE0, and BH&HLYP) and B (M06-L, M06, M06-2X, and M06-HF) were shown to decrease as the amount of Hartree-Fock exact exchange (HFx) increases, in other words, overestimation of calculated J becomes more severe as the HFx increases. We further investigated the effect of HFx fraction of DFT functional on J value, spin contamination, and spin density distributions by comparing the B3LYP analogues containing different amount of HFx. It was revealed that spin contamination and spin densities at each atom increases as the HFx increases. Above all, newly developed BLYP-5 functional, which has 5% of HFx, was found to have the scaling factor of 1.029, indicating that calculated J values are very close to that of experimental values without scaling. BLYP-5 has potential to be utilized for accurate evaluation of intramolecular magnetic coupling constant (J) of diradicals linked by five- or six-membered aromatic ring couplers.

  9. Computational study of the rate constants and free energies of intramolecular radical addition to substituted anilines

    Directory of Open Access Journals (Sweden)

    Andreas Gansäuer

    2013-08-01

    Full Text Available The intramolecular radical addition to aniline derivatives was investigated by DFT calculations. The computational methods were benchmarked by comparing the calculated values of the rate constant for the 5-exo cyclization of the hexenyl radical with the experimental values. The dispersion-corrected PW6B95-D3 functional provided very good results with deviations for the free activation barrier compared to the experimental values of only about 0.5 kcal mol−1 and was therefore employed in further calculations. Corrections for intramolecular London dispersion and solvation effects in the quantum chemical treatment are essential to obtain consistent and accurate theoretical data. For the investigated radical addition reaction it turned out that the polarity of the molecules is important and that a combination of electrophilic radicals with preferably nucleophilic arenes results in the highest rate constants. This is opposite to the Minisci reaction where the radical acts as nucleophile and the arene as electrophile. The substitution at the N-atom of the aniline is crucial. Methyl substitution leads to slower addition than phenyl substitution. Carbamates as substituents are suitable only when the radical center is not too electrophilic. No correlations between free reaction barriers and energies (ΔG‡ and ΔGR are found. Addition reactions leading to indanes or dihydrobenzofurans are too slow to be useful synthetically.

  10. Effect of Hartree-Fock exact exchange on intramolecular magnetic coupling constants of organic diradicals

    Energy Technology Data Exchange (ETDEWEB)

    Cho, Daeheum; Ko, Kyoung Chul; Lee, Jin Yong, E-mail: jinylee@skku.edu [Department of Chemistry, Sungkyunkwan University, Suwon 440-746 (Korea, Republic of); Ikabata, Yasuhiro; Wakayama, Kazufumi; Yoshikawa, Takeshi [Department of Chemistry and Biochemistry, School of Advanced Science and Engineering, Waseda University, 3-4-1 Okubo, Shinjuku-ku, Tokyo 169-8555 (Japan); Nakai, Hiromi, E-mail: nakai@waseda.jp [Department of Chemistry and Biochemistry, School of Advanced Science and Engineering, Waseda University, 3-4-1 Okubo, Shinjuku-ku, Tokyo 169-8555 (Japan); Research Institute for Science and Engineering, Waseda University, 3-4-1 Okubo, Shinjuku-ku, Tokyo 169-8555 (Japan); CREST, Japan Science and Technology Agency, Tokyo 102-0075 (Japan); Elements Strategy Initiative for Catalysts and Batteries (ESICB), Kyoto University, Katsura, Kyoto 615-8520 (Japan)

    2015-01-14

    The intramolecular magnetic coupling constant (J) of diradical systems linked with five- or six-membered aromatic rings was calculated to obtain the scaling factor (experimental J/calculated J ratio) for various density functional theory (DFT) functionals. Scaling factors of group A (PBE, TPSSh, B3LYP, B97-1, X3LYP, PBE0, and BH and HLYP) and B (M06-L, M06, M06-2X, and M06-HF) were shown to decrease as the amount of Hartree-Fock exact exchange (HFx) increases, in other words, overestimation of calculated J becomes more severe as the HFx increases. We further investigated the effect of HFx fraction of DFT functional on J value, spin contamination, and spin density distributions by comparing the B3LYP analogues containing different amount of HFx. It was revealed that spin contamination and spin densities at each atom increases as the HFx increases. Above all, newly developed BLYP-5 functional, which has 5% of HFx, was found to have the scaling factor of 1.029, indicating that calculated J values are very close to that of experimental values without scaling. BLYP-5 has potential to be utilized for accurate evaluation of intramolecular magnetic coupling constant (J) of diradicals linked by five- or six-membered aromatic ring couplers.

  11. Vibrational Spectroscopy of Intramolecular Hydrogen Bonds in the Infrared and Near-Infrared Regions

    DEFF Research Database (Denmark)

    Schrøder, Sidsel Dahl

    and 1,4-diaminobutane). Experimentally, the hydrogen bonds have been studied with vibrational spectroscopy in the infrared and near-infrared regions. The focus is primarily on spectra recorded in the near-infrared regions, which in these studies are dominated by O-H and N-H stretching overtones....... Overtone spectra have been recorded with intracavity laser photoacoustic laser spectroscopy and conventional long path absorption spectroscopy. Theoretically, a combination of electronic structure calculations and local mode models have been employed to guide the assignment of bands in the vibrational......,4-diaminobutane, no sign of intramolecular N-H···N hydrogen bonds were identified in the overtone spectra. However, theoretical analyzes indicate that intramolecular N-H···N hydrogen bonds are present in all three diamines if two hydrogen atoms on one of the methylene groups are substituted with triuoromethyl...

  12. On the nature of intramolecular vibrational energy transfer in dense molecular environments

    Energy Technology Data Exchange (ETDEWEB)

    Benten, Rebekka S. von [Institut fuer Physikalische Chemie der Universitaet Goettingen, Tammannstrasse 6, D-37077 Goettingen (Germany); Abel, Bernd, E-mail: Bernd.Abel@uni-lepzig.de [Wilhelm-Ostwald-Institut fuer Physikalische und Theoretische Chemie, Universitaet Leipzig, Linne-Strasse 2, D-04103 Leipzig (Germany)

    2010-12-09

    Graphical abstract: Mechanisms of IVR in multi-tiers of intramolecular energy levels in different molecular environments are investigated. - Abstract: Transient femtosecond-IR-pump-UV-absorption probe-spectroscopy has been employed to shed light on the nature of intramolecular vibrational energy transfer (IVR) in dense molecular environments ranging from the diluted gas phase to the liquid. A general feature in our experiments and those of others is that IVR proceeds via multiple timescales if overtones or combination vibrations of high frequency modes are excited. It has been found that collisions enhance IVR if its (slower) timescales can compete with collisions. This enhancement is, however, much more weaker and rather inefficient as opposed to the effect of collisions on intermolecular energy transfer which is well known. In a series of experiments we found that IVR depends not significantly on the average energy transferred in a collision but rather on the number of collisions. The collisions are much less efficient in affecting IVR than VET. We conclude that collision induced broadening of vibrational energy levels reduces the energy gaps and enhances existing couplings between tiers. The present results are an important step forward to rationalize and understand apparently different and not consistent results from different groups on different molecular systems between gas and liquid phases.

  13. Understanding perovskite formation through the intramolecular exchange method in ambient conditions

    Science.gov (United States)

    Szostak, Rodrigo; Castro, Jhon A. P.; Marques, Adriano S.; Nogueira, Ana F.

    2017-04-01

    Among the methods to prepare hybrid organic-inorganic perovskite films, the intramolecular exchange method was the first one that made possible to prepare perovskite solar cells with efficiencies higher than 20%. However, perovskite formation by this method is not completely understood, especially in ambient conditions. In this work, perovskite films were prepared by the intramolecular exchange method in ambient conditions. The spin coating speed and the frequency of the MAI solution dripping onto PbI2(DMSO) were varied during the deposition steps. With the combination of these two parameters, a rigid control of the solvent drying was possible. Thus, depending on the chosen conditions, the intermediate MAPb3I8·2DMSO was formed with residual PbI2. Otherwise, direct formation of perovskite film was attained. A mechanism for the direct formation of bulk perovskite was proposed. We also investigated how the posterior thermal annealing affects the crystallinity and defects in perovskite films. With prolonged thermal annealing, the excess of MAI can be avoided, increasing the efficiency and decreasing the hysteresis of the solar cells. The best perovskite solar cell achieved a stabilized power output of 12.9%. The findings of this work pave the way for realizing the fabrication of efficient perovskite solar cells in ambient atmosphere, a very desirable condition for cost-efficient large scale manufacturing of this technology.

  14. Instantaneous normal mode analysis for intermolecular and intramolecular vibrations of water from atomic point of view.

    Science.gov (United States)

    Chen, Yu-Chun; Tang, Ping-Han; Wu, Ten-Ming

    2013-11-28

    By exploiting the instantaneous normal mode (INM) analysis for models of flexible molecules, we investigate intermolecular and intramolecular vibrations of water from the atomic point of view. With two flexible SPC/E models, our investigations include three aspects about their INM spectra, which are separated into the unstable, intermolecular, bending, and stretching bands. First, the O- and H-atom contributions in the four INM bands are calculated and their stable INM spectra are compared with the power spectra of the atomic velocity autocorrelation functions. The unstable and intermolecular bands of the flexible models are also compared with those of the SPC/E model of rigid molecules. Second, we formulate the inverse participation ratio (IPR) of the INMs, respectively, for the O- and H-atom and molecule. With the IPRs, the numbers of the three species participated in the INMs are estimated so that the localization characters of the INMs in each band are studied. Further, by the ratio of the IPR of the H atom to that of the O atom, we explore the number of involved OH bond per molecule participated in the INMs. Third, by classifying simulated molecules into subensembles according to the geometry of their local environments or their H-bond configurations, we examine the local-structure effects on the bending and stretching INM bands. All of our results are verified to be insensible to the definition of H-bond. Our conclusions about the intermolecular and intramolecular vibrations in water are given.

  15. International Symposium on Spacecraft Ground Control and Flight Dynamics, SCD1, Sao Jose dos Campos, Brazil, Feb. 7-11, 1994

    Science.gov (United States)

    Rozenfeld, Pawel; Kuga, Helio Koiti; Orlando, Valcir

    An international symposium on spacecraft flight dynamics and ground control systems produced 85 papers in the areas of attitude determination and control, orbit control, satellite constellation strategies, stationkeeping, spacecraft maneuvering, orbit determination, astrodynamics, ground command and control systems, and mission operations. Several papers included discussions on the application of artificial intelligence, neural networks, expert systems, and ion propulsion. For individual titles, see A95-89098 through A95-89182.

  16. Level and dynamics of internal dose from 137Cs and 90Sr formation in connection with ecological diversity of polluted agrogenoses of Ukraine

    International Nuclear Information System (INIS)

    Kravets, A.P.; Grodzinsky, D.M.; Pavlenko, Yu.A.

    2004-01-01

    The purpose of our calculations was estimation of quantitative influence of ecological diversity on levels and dynamics of internal doses formation from long-lived radionuclide such as 137 Cs and 90 Sr. Our estimations have radioecological nature that is they are based on registration of natural mechanisms of agricultural products pollution. It has been realized on the basis of three-module ecological model of assessment of radiological consequences (EMARC) of use of polluted agrocenoses

  17. Medium-Ring Effects on the Endo/Exo Selectivity of the Organocatalytic Intramolecular Diels-Alder Reaction.

    Science.gov (United States)

    Hooper, Joel F; James, Natalie C; Bozkurt, Esra; Aviyente, Viktorya; White, Jonathan M; Holland, Mareike C; Gilmour, Ryan; Holmes, Andrew B; Houk, K N

    2015-12-18

    The intramolecular Diels-Alder reaction has been used as a powerful method to access the tricyclic core of the eunicellin natural products from a number of 9-membered-ring precursors. The endo/exo selectivity of this reaction can be controlled through a remarkable organocatalytic approach, employing MacMillan's imidazolidinone catalysts, although the mechanistic origin of this selectivity remains unclear. We present a combined experimental and density functional theory investigation, providing insight into the effects of medium-ring constraints on the organocatalyzed intramolecular Diels-Alder reaction to form the isobenzofuran core of the eunicellins.

  18. An Intramolecular Heck reaction that Prefers a 5-endo- to a 6-exo-trig Cyclization Pathway

    DEFF Research Database (Denmark)

    Vital, Paulo; Norrby, Per-Ola; Tanner, David Ackland

    2006-01-01

    A regioselective aromatic Claisen rearrangement was used to prepare 17a, the precursor of triflate 17e. The intramolecular Heck reaction of 17e is promoted only by bidentate phosphine ligands, giving exclusively and in excellent yield 20, the product of a 5-endo-trig cyclization, despite the poss......A regioselective aromatic Claisen rearrangement was used to prepare 17a, the precursor of triflate 17e. The intramolecular Heck reaction of 17e is promoted only by bidentate phosphine ligands, giving exclusively and in excellent yield 20, the product of a 5-endo-trig cyclization, despite...

  19. Short-Term Therapeutic Efficacy of the Isobar TTL Dynamic Internal Fixation System for the Treatment of Lumbar Degenerative Disc Diseases.

    Science.gov (United States)

    Qian, Jiale; Bao, Zhaohua; Li, Xuefeng; Zou, Jun; Yang, Huilin

    2016-07-01

    At present, posterior interbody fusion surgery with pedicle internal fixation is the gold standard for the treatment of lumbar degenerative disc diseases. However, an increasing number of studies have shown that because fused lumbar vertebrae lose their physiological activity, the compensatory range of motion (ROM) of the adjacent levels increases. To address this issue, dynamic internal fixation systems have been developed. Our goal was to investigate the short-term therapeutic efficacy of the Isobar TTL dynamic internal fixation system for the treatment of lumbar degenerative disc diseases and its effect on the ROM of the surgical segments. Retrospective Evaluation. Tertiary hospital setting in China. Twenty-four lumbar degenerative disc disease patients who underwent posterior lumbar decompression and single-segment Isobar TTL dynamic internal fixation at our hospital between January 2013 and July 2014 were retrospectively analyzed. The preoperative and one month, 3 month, and 12 month postoperative visual analog scale (VAS) pain scores, Japanese Orthopedic Association (JOA) scores, and Oswestry Disability Index (ODI) scores were observed and recorded to assess the clinical therapeutic effect; the lumbar ROM was measured preoperatively and at the last follow-up to evaluate the preservation of functional movement in the dynamically stabilized segment. All patients underwent the operation successfully without complications during hospitalization and were followed for 12 to 27 months, with an average of 18 months. The patients' preoperative and one month, 3 month, and 12 month postoperative VAS scores were 6.42 ± 0.72, 1.71 ± 0.86, 1.38 ± 0.65, and 1.37 ± 0.58, respectively, and their JOA scores were 9.54 ± 1.89, 21.21 ± 1.98, 22.50 ± 1.47, and 23.46 ± 1.32, respectively. The preoperative ODI score was 42.04 ± 2.63; the one month, 3 month, and 12 month postoperative ODI scores were 22.79 ± 1.61, 18.63 ± 1.61, and 15.08 ± 1.21, respectively. These

  20. NMR Spectroscopy and Molecular Dynamics Simulation of r(CCGCUGCGG)2 Reveal a Dynamic UU Internal Loop Found in Myotonic Dystrophy Type 1†

    Science.gov (United States)

    Parkesh, Raman; Fountain, Matthew; Disney, Matthew D.

    2011-01-01

    The NMR structure of an RNA with a copy of the 5′CUG/3′GUC motif found in the triplet repeating disorder myotonic dystrophy type 1 (DM1) is disclosed. The lowest energy conformation of the UU pair is a single hydrogen bonded structure; however, the UU protons undergo exchange indicating structural dynamics. Molecular dynamics simulations show that the single hydrogen bonded structure is the most populated one but the UU pair interconverts between 0, 1, and 2 hydrogen bonded pairs. These studies have implications for the recognition of the DM1 RNA by small molecules and proteins. PMID:21204525

  1. Structural effects on the electronic characteristics of intramolecularly intercalated alkali-rubrene complexes

    Energy Technology Data Exchange (ETDEWEB)

    Li, Tsung-Lung, E-mail: quantum@mail.ncyu.edu.tw [Department of Electrophysics, National Chia-Yi University, 300 Hsueh-Fu Road, Chiayi, 60004, Taiwan, ROC (China); Lu, Wen-Cai, E-mail: wencailu@jlu.edu.cn [Laboratory of Fiber Materials and Modern Textile, Growing Base for State Key Laboratory, College of Physics, Qingdao University, Qingdao, Shandong 266071 (China); State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun, Jilin 130021 (China)

    2016-11-01

    The geometric and electronic structures of neutral monolithium- and monosodium-rubrene (Li{sub 1} Rub and Na{sub 1} Rub) isomers are investigated and compared with monopotassium-rubrene (K{sub 1} Rub). Based on the alkali binding site, all isomers of these alkali-rubrene complexes can be subdivided into two types: intramolecularly intercalated and extramolecularly adsorbed. The minimum-energy Li{sub 1} Rub and Na{sub 1} Rub are intercalated structures, whereas the minimum-energy K{sub 1} Rub is adsorbed. The fact that the intercalated Li{sub 1} Rub and Na{sub 1} Rub structures are energetically favorable over the adsorbed ones can be explained by two energy rules. First, “double” proximity of the intercalating alkali element to a pair of phenyl side groups enormously reduces the total energy. Second, accommodation of a minuscule intercalant does not significantly deform the carbon frame and, thus, increases the energy only by a small amount. Additionally, the peculiar effects of intramolecular intercalation on the electronic structures of molecules are also studied in this simulation of monoalkali intercalation. In the monoalkali-intercalated rubrene complex, only one of the two pairs of phenyl groups of rubrene is intercalated, intentionally leaving another pair pristine, which facilitates the comparison of electronic structures between the intercalated and pristine pairs of phenyl side groups in a single molecule. The uniformity of chemical environments of the phenyl groups of the intercalated Li{sub 1} Rub/Na{sub 1} Rub is deteriorated by the incorporation of the intercalant, and leads to their spectral characteristics in contrast to K{sub 1} Rub. In particular, the introduction of the intercalant promotes the carbon 2p orbitals of the intercalated phenyl pair to take part in the electronic structures of the HOMO and LUMO peaks of Li{sub 1} Rub/Na{sub 1} Rub. The unpaired electron in the HOMO is delocalized over the backbone with higher probability of

  2. Structural effects on the electronic characteristics of intramolecularly intercalated alkali-rubrene complexes

    International Nuclear Information System (INIS)

    Li, Tsung-Lung; Lu, Wen-Cai

    2016-01-01

    The geometric and electronic structures of neutral monolithium- and monosodium-rubrene (Li 1 Rub and Na 1 Rub) isomers are investigated and compared with monopotassium-rubrene (K 1 Rub). Based on the alkali binding site, all isomers of these alkali-rubrene complexes can be subdivided into two types: intramolecularly intercalated and extramolecularly adsorbed. The minimum-energy Li 1 Rub and Na 1 Rub are intercalated structures, whereas the minimum-energy K 1 Rub is adsorbed. The fact that the intercalated Li 1 Rub and Na 1 Rub structures are energetically favorable over the adsorbed ones can be explained by two energy rules. First, “double” proximity of the intercalating alkali element to a pair of phenyl side groups enormously reduces the total energy. Second, accommodation of a minuscule intercalant does not significantly deform the carbon frame and, thus, increases the energy only by a small amount. Additionally, the peculiar effects of intramolecular intercalation on the electronic structures of molecules are also studied in this simulation of monoalkali intercalation. In the monoalkali-intercalated rubrene complex, only one of the two pairs of phenyl groups of rubrene is intercalated, intentionally leaving another pair pristine, which facilitates the comparison of electronic structures between the intercalated and pristine pairs of phenyl side groups in a single molecule. The uniformity of chemical environments of the phenyl groups of the intercalated Li 1 Rub/Na 1 Rub is deteriorated by the incorporation of the intercalant, and leads to their spectral characteristics in contrast to K 1 Rub. In particular, the introduction of the intercalant promotes the carbon 2p orbitals of the intercalated phenyl pair to take part in the electronic structures of the HOMO and LUMO peaks of Li 1 Rub/Na 1 Rub. The unpaired electron in the HOMO is delocalized over the backbone with higher probability of distributing over the central two fused rings than over the outer two

  3. Conserving Coherence and Storing Energy during Internal Conversion: Photoinduced Dynamics of cis- and trans-Azobenzene Radical Cations

    KAUST Repository

    Munkerup, Kristin; Romanov, Dmitri A.; Bohinski, Timothy; Stephansen, Anne B.; Levis, Robert J.; Sø lling, Theis Ivan

    2017-01-01

    Light harvesting via energy storage in azobenzene has been a key topic for decades, and the process of energy distribution over the molecular degrees of freedom following photoexcitation remains to be understood. Dynamics of a photoexcited system

  4. Intramolecular Valence and Spin Interaction in meso and rac Diastereomers of a p-Quinonoid-Bridged Diruthenium Complex

    Czech Academy of Sciences Publication Activity Database

    Kumbhakar, D.; Sarkar, B.; Maji, S.; Mobin, S. M.; Fiedler, Jan; Urbanos, F. A.; Jimenez-Aparicio, R.; Kaim, W.; Lahiri, G. K.

    2008-01-01

    Roč. 130, č. 51 (2008), s. 17575-17583 ISSN 0002-7863 R&D Projects: GA MŠk OC 139; GA MŠk LC510 Institutional research plan: CEZ:AV0Z40400503 Keywords : intramolecular valence * spin interaction * diruthenium complex Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 8.091, year: 2008

  5. Environment-sensitive quinolone demonstrating long-lived fluorescence and unusually slow excited-state intramolecular proton transfer kinetics

    Czech Academy of Sciences Publication Activity Database

    Zamotaiev, O. M.; Shvadchak, Volodymyr; Sych, T. P.; Melnychuk, N. A.; Yushchenko, Dmytro A.; Mely, Y.; Pivovarenko, V. G.

    2016-01-01

    Roč. 4, č. 3 (2016), č. článku 034004. ISSN 2050-6120 Institutional support: RVO:61388963 Keywords : quinolone * fluorescent probes * local polarity * hydration * excited-state intramolecular proton transfer * kinetics Subject RIV: CC - Organic Chemistry Impact factor: 2.656, year: 2016

  6. An intramolecular [2 + 2] cycloaddition of ketenimines via palladium-catalyzed rearrangements of N-allyl-ynamides.

    Science.gov (United States)

    DeKorver, Kyle A; Hsung, Richard P; Song, Wang-Ze; Wang, Xiao-Na; Walton, Mary C

    2012-06-15

    A cascade of Pd-catalyzed N-to-C allyl transfer-intramolecular ketenimine-[2 + 2] cycloadditions of N-allyl ynamides is described. This tandem sequence is highly stereoselective and the [2 + 2] cycloaddition could be rendered in a crossed or fused manner depending on alkene substitutions, leading to bridged and fused bicycloimines.

  7. On Hydrogen Bonding in the Intramolecularly Chelated Taitomers of Enolic Malondialdehyde and its Mono- and Dithio-Analogues

    DEFF Research Database (Denmark)

    Carlsen, Lars; Duus, Fritz

    1980-01-01

    The intramolecular hydrogen bondings in enolic malondialdehyde and it mono- and dithio-analogues have been evaluated by a semiempricial SCF–MO–CNDO method. The calculations predict that the hydrogen bonds play an important part in the stabilities of malondialdehyde and monothiomalondialdehyde...

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

    DEFF Research Database (Denmark)

    Tanner, David Ackland; Hagberg, Lars

    1998-01-01

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

  9. Synthesis of 1-indanones through the intramolecular Friedel-Crafts acylation reaction using NbCl5 as Lewis acid

    International Nuclear Information System (INIS)

    Polo, Ellen Christine; Silva-Filho, Luiz Carlos da; Silva, Gil Valdo Jose da; Constantino, Mauricio Gomes

    2008-01-01

    The intramolecular Friedel-Crafts acylation reaction of 3-arylpropanoic acids to give 1-indanones can be effected in good yields under mild conditions (room temperature) by using niobium pentachloride. Our results indicate that NbCl 5 acts both as reagent (to transform carboxylic acids into acyl chlorides) and as catalyst in the Friedel-Crafts cyclization. (author)

  10. An efficient and green synthesis of 1-indanone and 1-tetralone via intramolecular Friedel-Crafts acylation reaction

    DEFF Research Database (Denmark)

    Tran, Phuong Hoang; Huynh, Vy Hieu; Hansen, Poul Erik

    2015-01-01

    Metal-triflate-catalyzed intramolecular Friedel–Crafts acylation of 3-arylpropanoic and 4-arylbutanoic acids in triflate-anion ionic liquids under monomodal microwave irradiation is reported. The environmentally benign synthetic procedure allows the formation of cyclic ketones in good yields with...

  11. Approach to Interfacial and Intramolecular Electron Transfer of the Diheme Protein Cytochrome c(4) Assembled on Au(111) Surfaces

    DEFF Research Database (Denmark)

    Chi, Qijin; Zhang, Jingdong; Taner, Arslan

    2010-01-01

    in homogeneous solution for which kinetic analysis clearly testifies to electrostatic cooperative effects but no intramolecular, interheme ET higher than 0.1-10 s(-1). This difference suggests a strong gating feature of the process. On the basis of the three-dimensional structure of P. stutzeri cyt c(4), gating...

  12. Unusual NHC-Iridium(I) Complexes and Their Use in the Intramolecular Hydroamination of Unactivated Aminoalkenes

    KAUST Repository

    Sipos, Gellé rt; Ou, Arnold; Skelton, Brian W.; Falivene, Laura; Cavallo, Luigi; Dorta, Reto

    2016-01-01

    N-heterocyclic carbene (NHC) ligands with naphthyl side chains were employed for the synthesis of unsaturated, yet isolable [(NHC)Ir(cod)]+ (cod=1,5-cyclooctadiene) complexes. These compounds are stabilised by an interaction of the aromatic wingtip that leads to a sideways tilt of the NHC-Ir bond. Detailed studies show how the tilting of such N-heterocyclic carbenes affects the electronic shielding properties of the carbene carbon atom and how this is reflected by significant upfield shifts in the 13CNMR signals. When employed in the intramolecular hydroamination, these [(NHC)Ir(cod)]+ species show very high catalytic activity under mild reaction conditions. An enantiopure version of the catalyst system produces pyrrolidines with excellent enantioselectivities. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Intramolecular synergistic effect of glutamic acid, cysteine and glycine against copper corrosion in hydrochloric acid solution

    International Nuclear Information System (INIS)

    Zhang Daquan; Xie Bin; Gao Lixin; Cai Qirui; Joo, Hyung Goun; Lee, Kang Yong

    2011-01-01

    The corrosion protection of copper by glutamic acid, cysteine, glycine and their derivative (glutathione) in 0.5 M hydrochloric acid solution has been studied by the electrochemical impedance spectroscopy and cyclic voltammetry. The inhibition efficiency of the organic inhibitors on copper corrosion increases in the order: glutathione > cysteine > cysteine + glutamic acid + glycine > glutamic acid > glycine. Maximum inhibition efficiency for cysteine reaches about 92.9% at 15 mM concentration level. The glutathione can give 96.4% inhibition efficiency at a concentration of 10 mM. The molecular structure parameters were obtained by PM3 (Parametric Method 3) semi-empirical calculation. The intramolecular synergistic effect of glutamic acid, cysteine and glycine moieties in glutathione is attributed to the lower energy of the lowest unoccupied molecular orbital (E LUMO ) level and to the excess hetero-atom adsorption centers and the bigger coverage on the copper surface.

  14. Negative resists for i-line lithography utilizing acid-catalyzed intramolecular dehydration reaction

    Science.gov (United States)

    Ueno, Takumi; Uchino, Shou-ichi; Hattori, Keiko T.; Onozuka, Toshihiko; Shirai, Seiichiro; Moriuchi, Noboru; Hashimoto, Michiaki; Koibuchi, S.

    1994-05-01

    Chemical amplification negative resist system composed of a novolak resin, a carbinol and an acid generator is investigated for i-line phase-shift lithography. The reaction in this resist is based on an acid-catalyzed intramolecular dehydration reaction. The dehydration products act as aqueous-base dissolution inhibitors, and carbinol compounds in unexposed areas work as dissolution promoters. The resist composed of a novolak resin, 1,4-bis((alpha) -hydroxyisopropyl) benzene (DIOL-1) and 2- naphthoylmethyltetramethylenesulfonium triflate (PAG-2) gives the best lithographic performance in terms of sensitivity and resolution. Line-and-space patterns of 0.275 micrometers are obtained using an i-line stepper (NA:0.45) in conjunction with a phase shifting mask.

  15. Voltage Losses in Organic Solar Cells: Understanding the Contributions of Intramolecular Vibrations to Nonradiative Recombinations

    KAUST Repository

    Chen, Xiankai

    2017-12-18

    The large voltage losses usually encountered in organic solar cells significantly limit the power conversion efficiencies (PCEs) of these devices, with the result that the current highest PCE values in single-junction organic photovoltaic remain smaller than for other solar cell technologies, such as crystalline silicon or perovskite solar cells. In particular, the nonradiative recombinations to the electronic ground state from the lowest-energy charge-transfer (CT) states at the donor-acceptor interfaces in the active layer of organic devices, are responsible for a significant part of the voltage losses. Here, to better comprehend the nonradiative voltage loss mechanisms, a fully quantum-mechanical rate formula is employed within the framework of time-dependent perturbation theory, combined with density functional theory. The objective is to uncover the specific contributions of intramolecular vibrations to the CT-state nonradiative recombinations in several model systems, which include small-molecule and polymer donors as well as fullerene and nonfullerene acceptors.

  16. Rotational Isomers, Intramolecular Hydrogen Bond, and IR Spectra of o-Vinylphenol Homologs

    Science.gov (United States)

    Glazunov, V. P.; Berdyshev, D. V.; Balaneva, N. N.; Radchenko, O. S.; Novikov, V. L.

    2018-03-01

    The ν(OH) stretching-mode bands in solution IR spectra of five o-vinylphenol (o-VPh) homologs in the slightly polar solvents CCl4 and n-hexane were studied. Several rotamers with free OH groups were found in solutions of o-VPh and its methyl-substituted derivatives in n-hexane. The proportion of rotamers in o-VPh homologs with intramolecular hydrogen bonds (IHBs) O-H...π varied from 22 to 97% in the gas and cyclohexane according to B3LYP/cc-pVTZ calculations. The theoretically estimated effective enthalpies -ΔH of their IHBs varied in the range 0.20-2.24 kcal/mol.

  17. Intramolecular migration of amide hydrogens in protonated peptides upon collisional activation

    DEFF Research Database (Denmark)

    Jørgensen, Thomas J. D.; Gårdsvoll, H.; Ploug, M.

    2005-01-01

    Presently different opinions exist as to the degree of scrambling of amide hydrogens in gaseous protonated peptides and proteins upon collisional activation in tandem mass spectrometry experiments. This unsettled controversy is not trivial, since only a very low degree of scrambling is tolerable...... if collision-induced dissociation (CID) should provide reliable site-specific information from (1)H/(2)H exchange experiments. We have explored a series of unique, regioselectively deuterium-labeled peptides as model systems to probe for intramolecular amide hydrogen migration under low-energy collisional...... are protected against exchange with the solvent, while the amide hydrogens of the nonbinding sequences exchange rapidly with the solvent. We have utilized such long-lived complexes to generate peptides labeled with deuterium in either the binding or nonbinding region, and the expected regioselectivity...

  18. Functional analysis of propeptide as an intramolecular chaperone for in vivo folding of subtilisin nattokinase.

    Science.gov (United States)

    Jia, Yan; Liu, Hui; Bao, Wei; Weng, Meizhi; Chen, Wei; Cai, Yongjun; Zheng, Zhongliang; Zou, Guolin

    2010-12-01

    Here, we show that during in vivo folding of the precursor, the propeptide of subtilisin nattokinase functions as an intramolecular chaperone (IMC) that organises the in vivo folding of the subtilisin domain. Two residues belonging to β-strands formed by conserved regions of the IMC are crucial for the folding of the subtilisin domain through direct interactions. An identical protease can fold into different conformations in vivo due to the action of a mutated IMC, resulting in different kinetic parameters. Some interfacial changes involving conserved regions, even those induced by the subtilisin domain, blocked subtilisin folding and altered its conformation. Insight into the interaction between the subtilisin and IMC domains is provided by a three-dimensional structural model. Copyright © 2010 Federation of European Biochemical Societies. Published by Elsevier B.V. All rights reserved.

  19. Unusual NHC-Iridium(I) Complexes and Their Use in the Intramolecular Hydroamination of Unactivated Aminoalkenes

    KAUST Repository

    Sipos, Gellért

    2016-04-10

    N-heterocyclic carbene (NHC) ligands with naphthyl side chains were employed for the synthesis of unsaturated, yet isolable [(NHC)Ir(cod)]+ (cod=1,5-cyclooctadiene) complexes. These compounds are stabilised by an interaction of the aromatic wingtip that leads to a sideways tilt of the NHC-Ir bond. Detailed studies show how the tilting of such N-heterocyclic carbenes affects the electronic shielding properties of the carbene carbon atom and how this is reflected by significant upfield shifts in the 13CNMR signals. When employed in the intramolecular hydroamination, these [(NHC)Ir(cod)]+ species show very high catalytic activity under mild reaction conditions. An enantiopure version of the catalyst system produces pyrrolidines with excellent enantioselectivities. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Spectroscopy and intramolecular relaxation of methyl salicylate in its first excited singlet state

    Science.gov (United States)

    Kuper, Jerry W.; Perry, David S.

    1984-05-01

    High resolution fluorescence excitation experiments are reported for the blue emitting rotamer of methyl salicylate in its first excited singlet state. These experiments employ moderate expansions of methyl salicylate seeded in argon ( P0D=5-8 Torr cm) to achieve rotational and vibrational cooling in a pulsed supersonic jet. The rotational contour of the electronic origin at 30 055.3 cm-1 is shown to be consistent with a geometrically distorted π-π* excited state, partially polarized along the A axis and with a rotational temperature of 5-7 K. A noticeable broadening of the spectral features beyond the rotational contour begins at 500 cm-1 above the origin and then increases rapidly above 900 cm-1 reaching a width of 12 cm-1 near 1200 cm-1. The constancy of fluorescence decay lifetimes in this region indicate that intramolecular vibrational relaxation in the S1 manifold is the broadening mechanism.

  1. Tether-directed synthesis of highly substituted oxasilacycles via an intramolecular allylation employing allylsilanes

    Directory of Open Access Journals (Sweden)

    Cox Liam R

    2007-02-01

    Full Text Available Abstract Background Using a silyl tether to unite an aldehyde electrophile and allylsilane nucleophile into a single molecule allows a subsequent Lewis-acid-mediated allylation to proceed in an intramolecular sense and therefore receive all the benefits associated with such processes. However, with the ability to cleave the tether post allylation, a product that is the result of a net intermolecular reaction can be obtained. In the present study, four diastereoisomeric β-silyloxy-α-methyl aldehydes, which contain an allylsilane tethered through the β-carbinol centre, have been prepared, in order to probe how the relative configuration of the two stereogenic centres affects the efficiency and selectivity of the intramolecular allylation. Results Syn-aldehydes, syn-4a and syn-4b, both react poorly, affording all four possible diastereoisomeric oxasilacycle products. In contrast, the anti aldehydes anti-4a and anti-4b react analogously to substrates that lack substitution at the α-site, affording only two of the four possible allylation products. Conclusion The outcome of the reaction with anti-aldehydes is in accord with reaction proceeding through a chair-like transition state (T.S.. In these systems, the sense of 1,3-stereoinduction can be rationalised by the aldehyde electrophile adopting a pseudoaxial orientation, which will minimise dipole-dipole interactions in the T.S. The 1,4-stereoinduction in these substrates is modest and seems to be modulated by the R substituent in the starting material. In the case of the syn-substrates, cyclisation through a chair T.S. is unlikely as this would require the methyl substituent α to the reacting carbonyl group to adopt an unfavourable pseudoaxial position. It is therefore proposed that these substrates react through poorly-defined T.S.s and consequently exhibit essentially no stereoselectivity.

  2. External Electric Field Effects on Excited-State Intramolecular Proton Transfer in 4'-N,N-Dimethylamino-3-hydroxyflavone in Poly(methyl methacrylate) Films.

    Science.gov (United States)

    Furukawa, Kazuki; Hino, Kazuyuki; Yamamoto, Norifumi; Awasthi, Kamlesh; Nakabayashi, Takakazu; Ohta, Nobuhiro; Sekiya, Hiroshi

    2015-09-17

    The external electric field effects on the steady-state electronic spectra and excited-state dynamics were investigated for 4'-N,N-(dimethylamino)-3-hydroxyflavone (DMHF) in a poly(methyl methacrylate) (PMMA) film. In the steady-state spectrum, dual emission was observed from the excited states of the normal (N*) and tautomer (T*) forms. Application of an external electric field of 1.0 MV·cm(-1) enhanced the N* emission and reduced the T* emission, indicating that the external electric field suppressed the excited-state intramolecular proton transfer (ESIPT). The fluorescence decay profiles were measured for the N* and T* forms. The change in the emission intensity ratio N*/T* induced by the external electric field is dominated by ESIPT from the Franck-Condon excited state of the N* form and vibrational cooling in potential wells of the N* and T* forms occurring within tens of picoseconds. Three manifolds of fluorescent states were identified for both the N* and T* forms. The excited-state dynamics of DMHF in PMMA films has been found to be very different from that in solution due to intermolecular interactions in a rigid environment.

  3. Influence of forced internal air circulation on airflow distribution and heat transfer in a gas double-dynamic solid-state fermentation bioreactor.

    Science.gov (United States)

    Chen, Hongzhang; Qin, Lanzhi; Li, Hongqiang

    2014-02-01

    Internal air circulation affects the temperature field distribution in a gas double-dynamic solid-state fermentation bioreactor (GDSFB). To enhance heat transfer through strengthening internal air circulation in a GDSFB, we put an air distribution plate (ADP) into the bioreactor and studied the effects of forced internal air circulation on airflow, heat transfer, and cellulase activity of Trichoderma viride L3. Results showed that ADP could help form a steady and uniform airflow distribution, and with gas-guide tubes, air reversal was formed inside the bioreactor, thus resulting in a smaller temperature difference between medium and air by enhancing convective heat transfer inside the bioreactor. Using an ADP of 5.35 % aperture ratio caused a 1 °C decrease in the average temperature difference during the solid-state fermentation process of T. viride L3. Meanwhile, the cellulase activity of T. viride L3 increased by 13.5 %. The best heat-transfer effect was attained when using an ADP of 5.35 % aperture ratio and setting the fan power to 125 V (4.81 W) in the gas double-dynamic solid-state fermentation (GDSF) process. An option of suitable aperture ratio and fan power may be conducive to ADPs' industrial amplification.

  4. Quantum-dynamical Modeling of the Rydberg to Valence Excited-State Internal Conversion in Cyclobutanone and Cyclopentanone

    Directory of Open Access Journals (Sweden)

    Møller K. B.

    2013-03-01

    Full Text Available In this paper we present 4-state, 5-dimensional Vibronic Coupling Hamiltonians for cyclobutanone and cyclopentanone. Wave packet calculations using these Hamiltonians reveal that for cyclobutanone the (n,3s to (n,π* internal conversion involves direct motion in nuclear modes coupling the two states leading to fast population transfer. For cyclopentanone, internal vibrational energy redistribution is a bottleneck for activating reactive nuclear modes leading to slower population transfer.

  5. Quantum-dynamical Modeling of the Rydberg to Valence Excited-State Internal Conversion in Cyclobutanone and Cyclopentanone

    DEFF Research Database (Denmark)

    Kuhlman, T. S.; Sauer, Stephan P. A.; Solling, T. I.

    2013-01-01

    In this paper we present 4-state, 5-dimensional Vibronic Coupling Hamiltonians for cyclobutanone and cyclopentanone. Wave packet calculations using these Hamiltonians reveal that for cyclobutanone the (n,3s) to (n,π*) internal conversion involves direct motion in nuclear modes coupling the two st...... states leading to fast population transfer. For cyclopentanone, internal vibrational energy redistribution is a bottleneck for activating reactive nuclear modes leading to slower population transfer....

  6. Exploration of zeroth-order wavefunctions and energies as a first step toward intramolecular symmetry-adapted perturbation theory

    Science.gov (United States)

    Gonthier, Jérôme F.; Corminboeuf, Clémence

    2014-04-01

    Non-covalent interactions occur between and within all molecules and have a profound impact on structural and electronic phenomena in chemistry, biology, and material science. Understanding the nature of inter- and intramolecular interactions is essential not only for establishing the relation between structure and properties, but also for facilitating the rational design of molecules with targeted properties. These objectives have motivated the development of theoretical schemes decomposing intermolecular interactions into physically meaningful terms. Among the various existing energy decomposition schemes, Symmetry-Adapted Perturbation Theory (SAPT) is one of the most successful as it naturally decomposes the interaction energy into physical and intuitive terms. Unfortunately, analogous approaches for intramolecular energies are theoretically highly challenging and virtually nonexistent. Here, we introduce a zeroth-order wavefunction and energy, which represent the first step toward the development of an intramolecular variant of the SAPT formalism. The proposed energy expression is based on the Chemical Hamiltonian Approach (CHA), which relies upon an asymmetric interpretation of the electronic integrals. The orbitals are optimized with a non-hermitian Fock matrix based on two variants: one using orbitals strictly localized on individual fragments and the other using canonical (delocalized) orbitals. The zeroth-order wavefunction and energy expression are validated on a series of prototypical systems. The computed intramolecular interaction energies demonstrate that our approach combining the CHA with strictly localized orbitals achieves reasonable interaction energies and basis set dependence in addition to producing intuitive energy trends. Our zeroth-order wavefunction is the primary step fundamental to the derivation of any perturbation theory correction, which has the potential to truly transform our understanding and quantification of non

  7. Exploration of zeroth-order wavefunctions and energies as a first step toward intramolecular symmetry-adapted perturbation theory

    International Nuclear Information System (INIS)

    Gonthier, Jérôme F.; Corminboeuf, Clémence

    2014-01-01

    Non-covalent interactions occur between and within all molecules and have a profound impact on structural and electronic phenomena in chemistry, biology, and material science. Understanding the nature of inter- and intramolecular interactions is essential not only for establishing the relation between structure and properties, but also for facilitating the rational design of molecules with targeted properties. These objectives have motivated the development of theoretical schemes decomposing intermolecular interactions into physically meaningful terms. Among the various existing energy decomposition schemes, Symmetry-Adapted Perturbation Theory (SAPT) is one of the most successful as it naturally decomposes the interaction energy into physical and intuitive terms. Unfortunately, analogous approaches for intramolecular energies are theoretically highly challenging and virtually nonexistent. Here, we introduce a zeroth-order wavefunction and energy, which represent the first step toward the development of an intramolecular variant of the SAPT formalism. The proposed energy expression is based on the Chemical Hamiltonian Approach (CHA), which relies upon an asymmetric interpretation of the electronic integrals. The orbitals are optimized with a non-hermitian Fock matrix based on two variants: one using orbitals strictly localized on individual fragments and the other using canonical (delocalized) orbitals. The zeroth-order wavefunction and energy expression are validated on a series of prototypical systems. The computed intramolecular interaction energies demonstrate that our approach combining the CHA with strictly localized orbitals achieves reasonable interaction energies and basis set dependence in addition to producing intuitive energy trends. Our zeroth-order wavefunction is the primary step fundamental to the derivation of any perturbation theory correction, which has the potential to truly transform our understanding and quantification of non

  8. Femtosecond dynamics of a non-steroidal anti-inflammatory drug (piroxicam) in solution: The involvement of twisting motion

    Science.gov (United States)

    Gil, Michał; Douhal, Abderrazzak

    2008-06-01

    In this contribution, we report on fast and ultrafast dynamics of a non-steroidal anti-inflammatory drug, piroxicam (PX), in methyl acetate (MAC) and triacetin (TAC), two solvents of different viscosities. The enol form of PX undergoes a femtosecond (shorter than 100 fs) electronically excited state intramolecular proton-transfer reaction to produce keto tautomers. These structures exhibit an internal twisting motion to generate keto rotamers in ˜2-5 ps, a time being longer in TAC. The transient absorption/emission spectrum is very broad indicating that the potential-energy surface at the electronically excited state is very flat, and reflecting the involvement of several coordinates along which the wavepacket of the fs-produced structures evolve.

  9. A review of a method for dynamic load distribution, dynamic modeling, and explicit internal force control when two serial link manipulators mutually lift and transport a rigid body object

    International Nuclear Information System (INIS)

    Unseren, M.A.

    1997-09-01

    The report reviews a method for modeling and controlling two serial link manipulators which mutually lift and transport a rigid body object in a three dimensional workspace. A new vector variable is introduced which parameterizes the internal contact force controlled degrees of freedom. A technique for dynamically distributing the payload between the manipulators is suggested which yields a family of solutions for the contact forces and torques the manipulators impart to the object. A set of rigid body kinematic constraints which restricts the values of the joint velocities of both manipulators is derived. A rigid body dynamical model for the closed chain system is first developed in the joint space. The model is obtained by generalizing the previous methods for deriving the model. The joint velocity and acceleration variables in the model are expressed in terms of independent pseudovariables. The pseudospace model is transformed to obtain reduced order equations of motion and a separate set of equations governing the internal components of the contact forces and torques. A theoretic control architecture is suggested which explicitly decouples the two sets of equations comprising the model. The controller enables the designer to develop independent, non-interacting control laws for the position control and internal force control of the system

  10. A review of a method for dynamic load distribution, dynamic modeling, and explicit internal force control when two serial link manipulators mutually lift and transport a rigid body object

    Energy Technology Data Exchange (ETDEWEB)

    Unseren, M.A.

    1997-09-01

    The report reviews a method for modeling and controlling two serial link manipulators which mutually lift and transport a rigid body object in a three dimensional workspace. A new vector variable is introduced which parameterizes the internal contact force controlled degrees of freedom. A technique for dynamically distributing the payload between the manipulators is suggested which yields a family of solutions for the contact forces and torques the manipulators impart to the object. A set of rigid body kinematic constraints which restricts the values of the joint velocities of both manipulators is derived. A rigid body dynamical model for the closed chain system is first developed in the joint space. The model is obtained by generalizing the previous methods for deriving the model. The joint velocity and acceleration variables in the model are expressed in terms of independent pseudovariables. The pseudospace model is transformed to obtain reduced order equations of motion and a separate set of equations governing the internal components of the contact forces and torques. A theoretic control architecture is suggested which explicitly decouples the two sets of equations comprising the model. The controller enables the designer to develop independent, non-interacting control laws for the position control and internal force control of the system.

  11. Experimental investigation of the fluid dynamic efficiency of a high performance multi-valve internal combustion engine during the intake phase: Influence of valve-valve interference phenomena

    Directory of Open Access Journals (Sweden)

    Algieri Angelo

    2013-01-01

    Full Text Available The purpose of the present work is the analysis of the fluid dynamic behavior of a high performance internal combustion engine during the intake phase. In particular, a four-valve spark-ignition engine has been characterized at the steady flow rig. Dimensionless discharge coefficients have been used to define the global fluid dynamic efficiency of the intake system, while the Laser Doppler Anemometry (LDA technique has been employed to evaluate the mean flow in the valve curtain area and to characterise the interference phenomena between the two intake valves. The investigation has shown the significant influence of the valve lift on the volumetric efficiency of the intake apparatus. Moreover, the experimental analysis has highlighted that the valve-valve interference phenomena have a relevant impact on the head breathability, on the flow development within the combustion chamber and on the velocity standard deviations.

  12. A model of turbocharger radial turbines appropriate to be used in zero- and one-dimensional gas dynamics codes for internal combustion engines modelling

    Energy Technology Data Exchange (ETDEWEB)

    Serrano, J.R.; Arnau, F.J.; Dolz, V.; Tiseira, A. [CMT-Motores Termicos, Universidad Politecnica de Valencia, Camino de Vera s/n, 46022 Valencia (Spain); Cervello, C. [Conselleria de Cultura, Educacion y Deporte, Generalitat Valenciana (Spain)

    2008-12-15

    The paper presents a model of fixed and variable geometry turbines. The aim of this model is to provide an efficient boundary condition to model turbocharged internal combustion engines with zero- and one-dimensional gas dynamic codes. The model is based from its very conception on the measured characteristics of the turbine. Nevertheless, it is capable of extrapolating operating conditions that differ from those included in the turbine maps, since the engines usually work within these zones. The presented model has been implemented in a one-dimensional gas dynamic code and has been used to calculate unsteady operating conditions for several turbines. The results obtained have been compared with success against pressure-time histories measured upstream and downstream of the turbine during on-engine operation. (author)

  13. Development and validation of the International Hidradenitis Suppurativa Severity Score System (IHS4), a novel dynamic scoring system to assess HS severity

    DEFF Research Database (Denmark)

    Zouboulis, C C; Tzellos, T; Kyrgidis, A

    2017-01-01

    BACKGROUND: A validated tool for the dynamic severity assessment of hidradenitis suppurativa/acne inversa (HS) is lacking. OBJECTIVES: To develop and validate a novel dynamic scoring system to assess the severity of HS. METHODS: A Delphi voting procedure was conducted among the members......, as well as examination for correlation (Spearman's rho) and agreement (Cohen's kappa) with existing scores, were engaged to recognize the variables for a new International HS4 (IHS4) that was established by a second Delphi round. RESULTS: Consensus HS4 was based on number of skin lesions, number of skin....... Three candidate scores were presented to the second Delphi round. The resulting IHS4 score is arrived at by the number of nodules (multiplied by 1) plus the number of abscesses (multiplied by 2) plus the number of draining tunnels (multiplied by 4). A total score of 3 or less signifies mild, 4...

  14. A model of turbocharger radial turbines appropriate to be used in zero- and one-dimensional gas dynamics codes for internal combustion engines modelling

    International Nuclear Information System (INIS)

    Serrano, J.R.; Arnau, F.J.; Dolz, V.; Tiseira, A.; Cervello, C.

    2008-01-01

    The paper presents a model of fixed and variable geometry turbines. The aim of this model is to provide an efficient boundary condition to model turbocharged internal combustion engines with zero- and one-dimensional gas dynamic codes. The model is based from its very conception on the measured characteristics of the turbine. Nevertheless, it is capable of extrapolating operating conditions that differ from those included in the turbine maps, since the engines usually work within these zones. The presented model has been implemented in a one-dimensional gas dynamic code and has been used to calculate unsteady operating conditions for several turbines. The results obtained have been compared with success against pressure-time histories measured upstream and downstream of the turbine during on-engine operation

  15. Multi-mode-multi-state quantum dynamics of key five-membered heterocycles: spectroscopy and ultrafast internal conversion

    International Nuclear Information System (INIS)

    Koeppel, H.; Gromov, E.V.; Trofimov, A.B.

    2004-01-01

    The multi-mode and multi-state vibronic interactions in the heterocyclic molecules furan, pyrrole, thiophene and their radical cations are investigated theoretically, employing a linear vibronic coupling scheme. The underlying system parameters are determined from large-scale ab initio computations. Previous time-independent dynamical calculations on the radical cations are extended by wave-packet propagations (using the MCTDH method) confirming the strong nonadiabatic coupling effects. For the singlet excited states of furan and thiophene quantum dynamical calculations are presented which go beyond the two-state approximation frequently applied in the literature. The characteristic spectral structures are well reproduced, especially in the case of furan. The implications of these results on the photochemical reaction dynamics of these species are discussed

  16. Dynamics of data flows on the low-activated vanadium alloy for thermonuclear power engineering (analysis of four international data bases)

    International Nuclear Information System (INIS)

    Shepelev, A.G.; Kurilo, Yu.P.; Krivchenko, O.V.

    2015-01-01

    The paper presents the results of scientometric analysis of data flows in the International Data Bases SCOPUS, INSPEC, INIS, MSCI over a period since 1971 to 2014 on low-activated vanadium alloys suitable for operation as structural materials under extremely hard conditions in the future fusion reactors. The data on the dynamics of publications and contributions in them from the scientists of different countries have been obtained. The types and languages of publications have been identified. The analysis shows that investigations on the low-activated vanadium alloys are of current importance

  17. Influence of internal thermal mass on the indoor thermal dynamics and integration of phase change materials in furniture for building energy storage

    DEFF Research Database (Denmark)

    Johra, Hicham; Heiselberg, Per Kvols

    2017-01-01

    The increasing share of intermittent renewable energy on the grid encourages researchers to develop demand-side management strategies. Passive heat storage in the indoor space is a promising solution to improve the building energy flexibility. It relies on an accurate control of the transient...... building temperature. However, many of the current numerical models for building energy systems assume empty rooms and do not account entirely for the internal thermal inertia of objects like furniture. This review article points out that such assumption is not valid for dynamic calculations...

  18. Estimation of error in maximal intensity projection-based internal target volume of lung tumors: a simulation and comparison study using dynamic magnetic resonance imaging.

    Science.gov (United States)

    Cai, Jing; Read, Paul W; Baisden, Joseph M; Larner, James M; Benedict, Stanley H; Sheng, Ke

    2007-11-01

    To evaluate the error in four-dimensional computed tomography (4D-CT) maximal intensity projection (MIP)-based lung tumor internal target volume determination using a simulation method based on dynamic magnetic resonance imaging (dMRI). Eight healthy volunteers and six lung tumor patients underwent a 5-min MRI scan in the sagittal plane to acquire dynamic images of lung motion. A MATLAB program was written to generate re-sorted dMRI using 4D-CT acquisition methods (RedCAM) by segmenting and rebinning the MRI scans. The maximal intensity projection images were generated from RedCAM and dMRI, and the errors in the MIP-based internal target area (ITA) from RedCAM (epsilon), compared with those from dMRI, were determined and correlated with the subjects' respiratory variability (nu). Maximal intensity projection-based ITAs from RedCAM were comparatively smaller than those from dMRI in both phantom studies (epsilon = -21.64% +/- 8.23%) and lung tumor patient studies (epsilon = -20.31% +/- 11.36%). The errors in MIP-based ITA from RedCAM correlated linearly (epsilon = -5.13nu - 6.71, r(2) = 0.76) with the subjects' respiratory variability. Because of the low temporal resolution and retrospective re-sorting, 4D-CT might not accurately depict the excursion of a moving tumor. Using a 4D-CT MIP image to define the internal target volume might therefore cause underdosing and an increased risk of subsequent treatment failure. Patient-specific respiratory variability might also be a useful predictor of the 4D-CT-induced error in MIP-based internal target volume determination.

  19. Dynamical analysis of a PWR internals using super-elements in an integrated 3-D model model. Part 2: dynamical tests and seismic analysis

    International Nuclear Information System (INIS)

    Jesus Miranda, C.A. de.

    1992-01-01

    The results of the test analysis (frequencies) for the isolated super-elements and for the developed 3-D model of the internals core support structures of a PWR research reactor are presented. Once certified of the model effectiveness for this type of analysis the seismic spectral analysis was performed. From the results can be seen that the structures are rigid for this load, isolated or together with the other in the 3-D model, and there are no impacts among them during the earthquake (OBE). (author)

  20. Intramolecular didehydro-Diels-Alder reaction and its impact on the structure-function properties of environmentally sensitive fluorophores.

    Science.gov (United States)

    Brummond, Kay M; Kocsis, Laura S

    2015-08-18

    Reaction discovery plays a vital role in accessing new chemical entities and materials possessing important function.1 In this Account, we delineate our reaction discovery program regarding the [4 + 2] cycloaddition reaction of styrene-ynes. In particular, we highlight our studies that lead to the realization of the diverging reaction mechanisms of the intramolecular didehydro-Diels-Alder (IMDDA) reaction to afford dihydronaphthalene and naphthalene products. Formation of the former involves an intermolecular hydrogen atom abstraction and isomerization, whereas the latter is formed via an unexpected elimination of H2. Forming aromatic compounds by a unimolecular elimination of H2 offers an environmentally benign alternative to typical oxidation protocols. We also include in this Account ongoing work focused on expanding the scope of this reaction, mainly its application to the preparation of cyclopenta[b]naphthalenes. Finally, we showcase the synthetic utility of the IMDDA reaction by preparing novel environmentally sensitive fluorophores. The choice to follow this path was largely influenced by the impact this reaction could have on our understanding of the structure-function relationships of these molecular sensors by taking advantage of a de novo construction and functionalization of the aromatic portion of these compounds. We were also inspired by the fact that, despite the advances that have been made in the construction of small molecule fluorophores, access to rationally designed fluorescent probes or sensors possessing varied and tuned photophysical, spectral, and chemical properties are still needed. To this end, we report our studies to correlate fluorophore structure with photophysical property relationships for a series of solvatochromic PRODAN analogs and viscosity-sensitive cyanoacrylate analogs. The versatility of this de novo strategy for fluorophore synthesis was demonstrated by showing that a number of functional groups could be installed at