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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 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.

  3. 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.

  4. 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

  5. Intramolecular vibrational dynamical barrier due to extremely irrational couplings

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    The intramolecular vibrational dynamics due to extremely irrational couplings is demonstrated by contrast to the resonance couplings, for the three-mode case of H2O as an example. The extremely irrational couplings are shown to impose such strong hindrance to intramolecular vibrational relaxation (IVR) that they act as barriers. They restrict the direct action/energy transfer between the two stretching modes, though they allow the transfer between a stretching and a bending modes. In contrast, the resonance is more mediated by the bending mode and leads to chaotic IVR. It is also shown that there is a region in the dynamical space in which resonance and extremely irrational couplings coexist.

  6. Excited-state intramolecular proton transfer to carbon atoms: nonadiabatic surface-hopping dynamics simulations.

    Science.gov (United States)

    Xia, Shu-Hua; Xie, Bin-Bin; Fang, Qiu; Cui, Ganglong; Thiel, Walter

    2015-04-21

    Excited-state intramolecular proton transfer (ESIPT) between two highly electronegative atoms, for example, oxygen and nitrogen, has been intensely studied experimentally and computationally, whereas there has been much less theoretical work on ESIPT to other atoms such as carbon. We have employed CASSCF, MS-CASPT2, RI-ADC(2), OM2/MRCI, DFT, and TDDFT methods to study the mechanistic photochemistry of 2-phenylphenol, for which such an ESIPT has been observed experimentally. According to static electronic structure calculations, irradiation of 2-phenylphenol populates the bright S1 state, which has a rather flat potential in the Franck-Condon region (with a shallow enol minimum at the CASSCF level) and may undergo an essentially barrierless ESIPT to the more stable S1 keto species. There are two S1/S0 conical intersections that mediate relaxation to the ground state, one in the enol region and one in the keto region, with the latter one substantially lower in energy. After S1 → S0 internal conversion, the transient keto species can return back to the S0 enol structure via reverse ground-state hydrogen transfer in a facile tautomerization. This mechanistic scenario is verified by OM2/MRCI-based fewest-switches surface-hopping simulations that provide detailed dynamic information. In these trajectories, ESIPT is complete within 118 fs; the corresponding S1 excited-state lifetime is computed to be 373 fs in vacuum. Most of the trajectories decay to the ground state via the S1/S0 conical intersection in the keto region (67%), and the remaining ones via the enol region (33%). The combination of static electronic structure computations and nonadiabatic dynamics simulations is expected to be generally useful for understanding the mechanistic photophysics and photochemistry of molecules with intramolecular hydrogen bonds.

  7. Internal Stark effect mediates intramolecular excited-state proton transfer in 3-hydroxyflavone derivatives

    Science.gov (United States)

    Klymchenko, Andriy S.; Demchenko, Alexander P.

    2002-12-01

    Internal Stark effect in electronic spectra is the effect that is observed when the electronic bands shift udner the influence of promixal charges. In order to study the possible involvement of this effect in modulating the intramolecular proton transfer reactions in the excited state, we designed and studied several derivatives of 3-hydroxyflavone. They include the species containing neutral and positively charged substituents in 6 position of chromone ring. These compounds were studied in solvents of different polarities. In these experiments the shifts of both normal and tautomer flurosence bands are clearly observed in a manner predicted by Stark effect theory. In addition, a dramatic effect of suppression by introduced charge of intramolecular excited-state proton transfer was observed.

  8. Local group modes and the dynamics of intramolecular energy transfer across a heavy atom

    OpenAIRE

    Lopez, Vicente; Fairen, Victor; Lederman, Steven M.; Marcus, R.A

    1986-01-01

    The dynamics of energy transfer is discussed for a model system in which two ligands are separated by a heavy atom. Numerical and analytical results are given for the case that each ligand is a CC. In the quasiperiodic regime, the dynamics are interpreted using perturbation theory. Local group modes involved in an intramolecular energy localization which can occur in this regime are identified. An approximate separation of the primarily ligand–ligand motions from the primarily ligand–metal–li...

  9. The interplay between inter- and intra-molecular dynamics in a series of alkylcitrates

    Energy Technology Data Exchange (ETDEWEB)

    Kipnusu, Wycliffe Kiprop [University of Leipzig, Germany; Kossack, Wilhelm [University of Leipzig, Germany; Iacob, Ciprian [University of Leipzig; Zeigermann, Philipp [University of Leipzig, Germany; Jasiurkowska, Malgorzata [University of Leipzig, Germany; Sangoro, Joshua R [ORNL; Valiullin, Rustem [University of Leipzig, Germany; Kremer, Friedrich [University of Leipzig

    2013-01-01

    The inter- and intra-molecular dynamics in a series of glass-forming alkylcitrates is studied by a combination of Broadband Dielectric Spectroscopy (BDS), Pulsed Field Gradient Nuclear Magnetic Resonance (PFG NMR), Fourier-Transform Infrared (FTIR) spectroscopy and Differential Scanning Calorimetry (DSC). Analyzing the temperature dependencies of specific IR absorption bands in terms of their spectral position and the corresponding oscillator strengths enables one to unravel the intramolecular dynamics of specific molecular moieties and to compare them with the (primarily dielectrically) determined intermolecular dynamics. With decreasing temperature, the IR band positions of carbonyls (part of the core units) and H-bonded moieties of citrates show a red shift with a kink at the calorimetric glass transition temperature (Tg) while other moieties, whose dynamics are decoupled from those of the core units, exhibit a blue shift with nominal changes at Tg. The oscillator strength of all units in citrates depicts stronger temperature dependencies above Tg and in some, the ester linkage and H-bonded units show a change of slope at a temperature where structural and faster secondary relaxations merge. By that, a wealth of novel information is obtained proving the fundamental importance of intramolecular mobility in the process of glass formation, beyond coarse-grained descriptions.

  10. Conformation and intramolecular relaxation dynamics of semiflexible randomly hyperbranched polymers

    Science.gov (United States)

    Kumar, Amit; Rai, Gobind Ji; Biswas, Parbati

    2013-03-01

    The conformational and dynamic properties of semiflexible randomly hyperbranched polymers are investigated in dilute solutions within the framework of optimized Rouse-Zimm formalism. Semiflexibility is incorporated by restricting the directions and orientations of the respective bond vectors, while hydrodynamic interactions are modeled through the preaveraged Oseen tensor. The effect of semiflexibility is typically reflected in the intermediate frequency regime of the viscoelastic relaxation moduli where the bond orientation angle restores the characteristic power-law scaling in fractal structures, as in randomly hyperbranched polymers. Despite the absence of this power-law scaling regime in flexible randomly hyperbranched polymers and in earlier models of semiflexible randomly branched polymers due to weak disorder [C. von Ferber and A. Blumen, J. Chem. Phys. 116, 8616 (2002)], 10.1063/1.1470198, this power-law behavior may be reinstated by explicitly modeling hyperbranched polymers as a Vicsek fractals. The length of this power-law zone in the intermediate frequency region is a combined function of the number of monomers and the degree of semiflexibility. A clear conformational transition from compact to open structures is facilitated by changing the bond orientation angle, where the compressed conformations are compact, while the expanded ones are relatively non-compact. The extent of compactness in the compressed conformations are much less compared to the semiflexible dendrimers, which resemble hard spheres. The fractal dimensions of the compressed and expanded conformations calculated from the Porod's scaling law vary as a function of the bond orientation angle, spanning the entire range of three distinct scaling regimes of linear polymers in three-dimensions. The results confirm that semiflexibility exactly accounts for the excluded volume interactions which are expected to be significant for such polymers with complex topologies.

  11. On the Intramolecular Hydrogen Bond in Solution: Car-Parrinello and Path Integral Molecular Dynamics Perspective.

    Science.gov (United States)

    Dopieralski, Przemyslaw; Perrin, Charles L; Latajka, Zdzislaw

    2011-11-08

    The issue of the symmetry of short, low-barrier hydrogen bonds in solution is addressed here with advanced ab initio simulations of a hydrogen maleate anion in different environments, starting with the isolated anion, going through two crystal structures (sodium and potassium salts), then to an aqueous solution, and finally in the presence of counterions. By Car-Parrinello and path integral molecular dynamics simulations, it is demonstrated that the position of the proton in the intramolecular hydrogen bond of an aqueous hydrogen maleate anion is entirely related to the solvation pattern around the oxygen atoms of the intramolecular hydrogen bond. In particular, this anion has an asymmetric hydrogen bond, with the proton always located on the oxygen atom that is less solvated, owing to the instantaneous solvation environment. Simulations of water solutions of hydrogen maleate ion with two different counterions, K(+) and Na(+), surprisingly show that the intramolecular hydrogen-bond potential in the case of the Na(+) salt is always asymmetric, regardless of the hydrogen bonds to water, whereas for the K(+) salt, the potential for H motion depends on the location of the K(+). It is proposed that repulsion by the larger and more hydrated K(+) is weaker than that by Na(+) and competitive with solvation by water.

  12. High resolution photoelectron spectroscopy and femtosecond intramolecular dynamics using supersonic molecular beams

    Energy Technology Data Exchange (ETDEWEB)

    Niu, B.

    1992-09-01

    High resolution He I[alpha] photoelectron spectroscopy of formaldehyde and ketene and their deuterated compounds, are reported. The combination of a (H2CO) double-pass high-resolution electron-energy analyzer and effective rotational cooling of the sample by supersonic expansion enable the spectroscopy of these molecular cations. The vibrational autocorrelation functions are calculated from the high-resolution photoelectron spectra, shedding light on the ultrafast intramolecular dynamics of the molecular cations. This study reveals much more vibrational structural detail in the first electronic excited state of H2CO cations. The first electronic excited state of H2CO cations may have nonplanar equilibrium geometry. Strong isotope effects on vibronic (vibrational) coupling are observed in the second electronic excited state of H2CO. Vibrational autocorrelation functions are calculated for all four observed electronic states of H2CO. The correlation function of the first electronic excited state of H2CO shows a slow decay rate on the femtosecond time scale. The ultrafast decay of the H2CO cations in the third electronic excited state implies that dissociation and intramolecular processes are the main decay pathways. The present spectra of the ground states of ketene cations have more fine structure than before. The AIEs of the first and fifth excited states are determined unambiguously more accurately. The doublet-like fine structures present in the lint excited state of ketene implies the excitation of a soft'' mode not observed before. The vibrational autocorrelation functions are calculated for 4 of the 6 observed electronic states. The dynamics of the ground states of the cations are characterized by a wave packet oscillating with small amplitude around the minimum on the upper PES. The decay dynamics of the first and the fifth excited states of ketene are characterized by ultra-fast intramolecular processes like predissociation.

  13. High resolution photoelectron spectroscopy and femtosecond intramolecular dynamics using supersonic molecular beams

    Energy Technology Data Exchange (ETDEWEB)

    Niu, B.

    1992-09-01

    High resolution He I{alpha} photoelectron spectroscopy of formaldehyde and ketene and their deuterated compounds, are reported. The combination of a (H2CO) double-pass high-resolution electron-energy analyzer and effective rotational cooling of the sample by supersonic expansion enable the spectroscopy of these molecular cations. The vibrational autocorrelation functions are calculated from the high-resolution photoelectron spectra, shedding light on the ultrafast intramolecular dynamics of the molecular cations. This study reveals much more vibrational structural detail in the first electronic excited state of H2CO cations. The first electronic excited state of H2CO cations may have nonplanar equilibrium geometry. Strong isotope effects on vibronic (vibrational) coupling are observed in the second electronic excited state of H2CO. Vibrational autocorrelation functions are calculated for all four observed electronic states of H2CO. The correlation function of the first electronic excited state of H2CO shows a slow decay rate on the femtosecond time scale. The ultrafast decay of the H2CO cations in the third electronic excited state implies that dissociation and intramolecular processes are the main decay pathways. The present spectra of the ground states of ketene cations have more fine structure than before. The AIEs of the first and fifth excited states are determined unambiguously more accurately. The doublet-like fine structures present in the lint excited state of ketene implies the excitation of a ``soft`` mode not observed before. The vibrational autocorrelation functions are calculated for 4 of the 6 observed electronic states. The dynamics of the ground states of the cations are characterized by a wave packet oscillating with small amplitude around the minimum on the upper PES. The decay dynamics of the first and the fifth excited states of ketene are characterized by ultra-fast intramolecular processes like predissociation.

  14. 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.

  15. 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.

  16. Electron diffraction analysis for the molecules with degenerate large amplitude motions: Intramolecular dynamics in arsenic pentafluoride

    Science.gov (United States)

    Kochikov, Igor V.; Kovtun, Dmitry M.; Tarasov, Yury I.

    2017-03-01

    There exists a noticeable disagreement in the difference of axial and equatorial bond lengths in D3h symmetry arsenic and phosphorus pentafluorides between the GED data and high level quantum chemical results. In order to resolve this disagreement, a new structural analysis of the original experiment of (Clippard & Bartell, Inorg. Chem., 9 (1970) 805-811) was undertaken on the basis of modern approach incorporating spectroscopic evidence and quantum chemical information and allowing for intramolecular large-amplitude motion. The results of the analysis prove the internal insufficiency of the experimental material in the description of the accurate positions of the peaks on the radial distribution function. Additional experimental investigation of pentahalide molecules, especially at high temperatures, is of interest.

  17. Excited state intramolecular proton transfer and charge transfer dynamics of a 2-(2'-hydroxyphenyl)benzoxazole derivative in solution.

    Science.gov (United States)

    Kim, Chul Hoon; Park, Jaehun; Seo, Jangwon; Park, Soo Young; Joo, Taiha

    2010-05-13

    Excited state intramolecular proton transfer (ESIPT) and subsequent intramolecular charge transfer (ICT) dynamics of a 2-(2'-hydroxyphenyl)benzoxazole derivative conjugated with an electron withdrawing group (HBOCE) in solutions and a polymer film has been investigated by femtosecond time-resolved fluorescence (TRF) and TRF spectra measurements without the conventional spectral reconstruction method. TRF with high enough resolution (benzoxazole groups is invoked to account for the dispersive ESIPT dynamics in liquids. From the TRF spectra of both the enol and keto isomers, we have identified the ICT reaction of the keto isomer occurring subsequent to the ESIPT. The ICT proceeds also by two time constants of near instantaneous and 2.7 ps. Since the ICT dynamics of HBOCE is rather close to the polar solvation dynamics, we argue that the ICT is barrierless and determined mostly by the solvent fluctuation.

  18. High resolution photoelectron spectroscopy and femtosecond intramolecular dynamics of H2CCO + and D2CCO +

    Science.gov (United States)

    Niu, Baohua; Bai, Ying; Shirley, David A.

    1993-08-01

    High resolution helium Iα (584 Å) photoelectron spectra of H2CCO and D2CCO are reported. The present spectra of the ground states of ketene cations show more vibrational fine structure than previously reported. The adiabatic ionization energies (AIEs) of the cations' first, second, and fifth excited states are determined unambiguously. The doubletlike fine structures present in the first excited states of ketene cations imply the excitation of a ``soft'' mode that was not observed before. It was assigned to the ν5 mode, which is characterized by the CH2 (CD2) group out-of-plane wagging motion. The complexity of the photoelectron spectra obtained for the ionic first excited states is attributed to the possible dissociation and predissociation of this state. Strong isotope effects are observed in the vibronic (vibrational) couplings in most of the ionic states. Vibrational autocorrelation functions are calculated from the high-resolution photoelectron spectra for four of the six ionic states observed. The dynamics of the ground states of the cations are characterized by a wave packet oscillating with small amplitude around the minimum of the upper potential energy surfaces (PES). The decay dynamics of the ionic first and fifth excited states of ketene are characterized by ultrafast intramolecular processes such as dissociation and predissociation.

  19. 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.

  20. Microsolvation and the Effects of Non-Covalent Interactions on Intramolecular Dynamics

    Science.gov (United States)

    Foguel, Lidor; Vealey, Zachary; Vaccaro, Patrick

    2017-06-01

    Physicochemical processes brought about by non-covalent interactions between neighboring molecules are undeniably of crucial importance in the world around us, being responsible for effects ranging from the subtle (yet precise) control of biomolecular recognition events to the very existence of condensed phases. Of particular interest is the differential ability of distinct non-covalent forces, such as those mediated by dispersion-dominated aryl (π-π) coupling and electrostatically-driven hydrogen bonding, to affect unimolecular transformations by altering potential surface topographies and the nature of reaction coordinates. A concerted experimental and computational investigation of "microsolvation" (solvation at the molecular level) has been undertaken to elucidate the site-specific coupling between solute and solvent degrees of freedom, as well as attendant consequences for the efficiency and pathway of intrinsic proton-transfer dynamics. Targeted species have been synthesized in situ under "cold" supersonic free-jet expansion conditions (T_{rot} ≈ 1-2K) by complexing an active (proton-transfer) substrate with various ligands (e.g., water isotopologs and benzene derivatives) for which competing interaction mechanisms can lead to unique binding motifs. A series of fluorescence-based spectroscopic measurements have been performed on binary adducts formed with the prototypical 6-hydroxy-2-formylfulvene (HFF) system, where a quasi-linear intramolecular O-H...O bond and a zero-point energy that straddles the proton-transfer barrier crest synergistically yield the largest tunneling-induced splitting ever reported for the ground electronic state of an isolated neutral molecule. Such characteristics afford a localized metric for unraveling incipient changes in unimolecular reactivity, with comparison of experimentally observed and quantum-chemical predicted rovibronic landscapes serving to discriminate complexes built upon electrostatic (hydrogen-bonding) and

  1. 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

  2. Relaxation dynamics in quantum dissipative systems: the microscopic effect of intramolecular vibrational energy redistribution.

    Science.gov (United States)

    Uranga-Piña, L; Tremblay, J C

    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

  3. The short-time intramolecular dynamics of solutes in liquids. II. Vibrational population relaxation

    Science.gov (United States)

    Goodyear, Grant; Stratt, Richard M.

    1997-08-01

    Events such as the vibrational relaxation of a solute are often well described by writing an effective equation of motion—a generalized Langevin equation—which expresses the surrounding medium's influence on the intramolecular dynamics in terms of a friction and a fluctuating force acting on the solute. These quantities, though, can be obtained from the instantaneous normal modes (INMs) of the system when the relaxation takes place in a fluid, suggesting that we should be able to analyze in some detail the solvent motions driving the relaxation, at least for short times. In this paper we show that this promise can indeed be realized for the specific case of a vibrating diatomic molecule dissolved in an atomic solvent. Despite the relatively long times typical of vibrational population relaxation, it turns out that understanding the behavior of the vibrational friction at the short times appropriate to INMs (a few hundred femtoseconds) often suffices to predict T1 times. We use this observation to probe the dependence of these relaxation rates on thermodynamic conditions and to look at the molecular mechanisms underlying the process. We find that raising the temperature at any given density or raising the density at any given temperature will invariably increase the rate of energy relaxation. However, since these two trends may be in conflict in a typical constant-pressure laboratory experiment, we also find that it is possible to make sense of the "anomalous" inverted temperature dependence recently seen experimentally. We find, as well, that the INM theory—which has no explicit collisions built into it—predicts exactly the same density dependence as the venerable independent-binary-collision (IBC) theory (an intriguing result in view of recent claims that experimental observations of this kind of dependence provide support for the IBC theory). The actual mechanisms behind vibrational population relaxation are revealed by looking in detail at the

  4. d-Orbital Effects on Stereochemical Non-Rigidity: Twisted Ti IV Intramolecular Dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Davis, Anna V.; Firman, Timothy K.; Hay, Benjamin P.; Raymond, Kenneth N.

    2006-07-26

    The isomerization dynamics of tris-catecholate complexes have been investigated by variable temperature NMR methods, demonstrating that the intramolecular racemization of ? and ? enantiomers of d0 TiIV is facile and faster than that of d10 GaIII and GeIV analogs. Activation parameters for the racemization of K2[Ti23] (H22 = 2,3-dihydroxy-N,N?-diisopropylterephthalamide) were determined from lineshape analysis of 1H NMR spectra (methanol-d4: ?H? = 47(1) kJ/mol; ?S? = -34(4) J/molK; ?G?298 = 57(3) kJ/mol; DMF-d7: ?H? = 55(1) kJ/mol; ?S? = -16(4) J/molK; ?G?298 = 59(3) kJ/mol; D2O (pD* = 8.6, 20% MeOD): ?H? = 48(3) kJ/mol; ?S? = -28(10) J/molK; ?G?298 = 56(3) kJ/mol). The study of K2[Ti43] (H24 = 2,3-dihydroxy-N-tert-butyl-N?-benzylterephthalamide) reveals two distinct isomerization processes: faster racemization of mer-[Ti43]2- by way of a Bailar twist mechanism (D3h transition state) (Tc ? 242 K, methanol-d4), and a slower mer/fac-[Ti43]2- isomerization by way of a R?y-Dutt mechanism (C2v transition state) (Tc ? 281 K, methanol-d4). The solution behavior of the TiIV complexes mirrors that reported previously for analogous GaIII complexes, while that of analogous GeIV complexes was too inert to be detected by 1H NMR up to 400 K. These experimental findings are augmented by DFT calculations of the ML3 grounds states and Bailar and R?y-Dutt transition states, which correctly predict the relative kinetic barriers of the three metal ions, in addition to faithfully reproducing the ground state structures. Orbital calculations support the conclusion that participation of the TiIV d0 orbitals in ligand bonding contributes to the greater stabilization of the prismatic TiIV transition states. Battelle operates the Pacific Northwest National Laboratory for the U.S. Department of Energy.

  5. Implications of dynamic imine chemistry for the sustainable synthesis of nitrogen heterocycles via transimination followed by intramolecular cyclisation.

    Science.gov (United States)

    Laha, Joydev K; Tummalapalli, K S Satyanarayana; Jethava, Krupal P

    2016-02-28

    An exploration of a tandem approach to the sustainable synthesis of N-heterocycles from readily available N-aryl benzylamines or imines and ortho-substituted anilines is described, which demonstrates, for the first time, an important synthetic application of dynamic imine chemistry. The key features to the successful development of this protocol include the utilisation of N-aryl benzylamines as imine precursors in transimination, the occurrence of transimination in acetonitrile in the absence of any catalysts, an intramolecular nucleophilic addition occurring in the newly formed imine causing irreversible transimination, and the tandem event occurring under green conditions.

  6. 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 *.

  7. Intramolecular hydrogen bond: Can it be part of the basis set of valence internal coordinates in normal mode analysis?

    Indian Academy of Sciences (India)

    Sarvesh Kumar Pandey; Prasanta Das; Puspendu K Das; Elangannan Arunan; Sadasivam Manogaran

    2015-06-01

    It has been shown earlier1 that the relaxed force constants (RFCs) could be used as a measure of bond strength only when the bonds form a part of the complete valence internal coordinates (VIC) basis. However, if the bond is not a part of the complete VIC basis, its RFC is not necessarily a measure of bond strength. Sometimes, it is possible to have a complete VIC basis that does not contain the intramolecular hydrogen bond (IMHB) as part of the basis. This means the RFC of IMHB is not necessarily a measure of bond strength. However, we know that IMHB is a weak bond and hence its RFC has to be a measure of bond strength. We resolve this problem of IMHB not being part of the complete basis by postulating `equivalent’ basis sets where IMHB is part of the basis at least in one of the equivalent sets of VIC. As long as a given IMHB appears in one of the equivalent complete VIC basis sets, its RFC could be used as a measure of bond strength parameter.

  8. INFLUENCE OF SOLVENT ON INTRAMOLECULAR PROTON-TRANSFER IN HYDROGEN MALONATE - MOLECULAR-DYNAMICS SIMULATION STUDY OF TUNNELING BY DENSITY-MATRIX EVOLUTION AND NONEQUILIBRIUM SOLVATION

    NARCIS (Netherlands)

    MAVRI, J; BERENDSEN, HJC; VANGUNSTEREN, WF

    1993-01-01

    A density matrix evolution (DME) method (Berendsen, H. J. C.; Mavri, J. J. Phys. Chem. the preceding paper in this issue) in combination with classical molecular dynamics simulation was applied to calculate the rate of proton tunneling in the intramolecular double-well hydrogen bond of hydrogen malo

  9. 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.

  10. Intramolecular SN2 reaction caused by photoionization of benzene chloride-NH3 complex: direct ab initio molecular dynamics study.

    Science.gov (United States)

    Tachikawa, Hiroto

    2006-01-12

    Ionization processes of chlorobenzene-ammonia 1:1 complex (PhCl-NH3) have been investigated by means of full dimensional direct ab initio molecular dynamics (MD) method, static ab initio calculations, and density functional theory (DFT) calculations. The static ab initio and DFT calculations of neutral PhCl-NH3 complex showed that one of the hydrogen atoms of NH3 orients toward a carbon atom in the para-position of PhCl. The dynamics calculation for ionization of PhCl-NH3 indicated that two reaction channels are competitive with each other as product channels: one is an intramolecular SN2 reaction expressed by a reaction scheme [PhCl-NH3]+-->SN2 intermediate complex-->PhNH3++Cl, and the other is ortho-NH3 addition complex (ortho complex) in which NH3 attacks the ortho-carbon of PhCl+ and the trajectory leads to a bound complex expressed by (PhCl-NH3)+. The mechanism of the ionization of PhCl-NH3 is discussed on the basis of the theoretical results.

  11. Spectroscopic probing of location and dynamics of an environment-sensitive intramolecular charge transfer probe within liposome membranes.

    Science.gov (United States)

    Paul, Bijan Kumar; Guchhait, Nikhil

    2011-11-15

    The present work demonstrates the interaction of an intramolecular charge transfer (ICT) probe 5-(4-dimethylamino-phenyl)-penta-2,4-dienoic acid methyl ester (DPDAME) with liposome membranes of dimyristoyl-L-α-phosphatidylcholine (DMPC) and dimyristoyl-L-α-phosphatidylglycerol (DMPG) studied by steady-state absorption, emission and time-resolved emission techniques. A huge hypsochromic shift together with remarkable enhancement of fluorescence quantum yield of the polarity sensitive ICT emission of DPDAME upon interaction with the lipids has been rationalized in terms of incorporation of the probe into hydrophobic interior of the lipids. Compelling evidences for penetration of the probe into the hydrocarbon interior of the lipids have been deduced from intertwining different experimental results e.g., micropolarity in the immediate vicinity of the probe in lipid environments, steady-state anisotropy, red-edge excitation shift (REES), fluorescence quenching experiments and time-resolved measurements. The rotational relaxation dynamics study of the membrane-bound probe unveils the impartation of high degree of motional rigidity. Wavelength-selective emission behaviour paves way for monitoring of solvent-relaxation in the membranes. Overall, the ICT probe DPDAME displays its commendable sensitivity in deciphering the microheterogeneous environments of liposomal membranes of DMPC and DMPG and promises a new membrane-polarity sensitizing probe.

  12. Intramolecular Three-Colour Single Pair FRET of Intrinsically Disordered Proteins with Increased Dynamic Range

    Science.gov (United States)

    Milles, Sigrid; Koehler, Christine; Gambin, Yann

    2012-01-01

    Single molecule observation of fluorescence resonance energy transfer can be used to provide insights 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. PMID:22739670

  13. 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.

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

    Science.gov (United States)

    Mori, Yukie; Masuda, Yuichi

    2015-09-01

    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 CCl4, acetonitrile, and dimethylsulfoxide solutions from the magnetic dipolar interactions between the 17O and 1H nuclei monitoring the nuclear magnetic relaxation times of 1H. The experimental results indicated that the H-bond geometry of 2 is influenced by the interactions with dimethylsulfoxide, suggesting the formation of a bifurcated H-bond, which was supported by the DFT calculations. The MD simulations for the methanol solution of 2 showed that the asymmetry of the OH distance is correlated with the asymmetry in the electrostatic field of the

  15. 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.

  16. 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.

  17. 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

  18. Car-Parrinello and path integral molecular dynamics study of the intramolecular hydrogen bonds in the crystals of benzoylacetone and dideuterobenzoylacetone.

    Science.gov (United States)

    Durlak, Piotr; Latajka, Zdzisław

    2014-11-14

    The dynamics of the intramolecular short hydrogen bond in the molecular crystal of benzoylacetone and its deuterated analogue are investigated using ab initio molecular dynamics simulations. A study on intramolecular hydrogen bonding in 1-phenyl-1,3-butadione (I) and 1-deuteroxy-2-deutero-1-phenylbut-1-en-3-one (II) crystals has been carried out at 160 K and 300 K on the CPMD method level and at 300 K on the PIMD method level. The analysis of the two-dimensional free-energy landscape of reaction coordinate δ-parameter and ROO distances shows that the hydrogen (deuter) between the two oxygen atoms adopts a slightly asymmetrical position in the single potential well. When the nuclear quantum effects are taken into account, very large delocalization of the bridging proton is observed. These studies indicate that hydrogen bonds in the crystal of benzoylacetone have characteristic properties for the type of bonding model resonance-assisted hydrogen bonds (RAHB) without existing the equilibrium of the two tautomers. The infrared spectrum has been calculated, and a comparative vibrational analysis has been performed. The CPMD vibrational results appear to qualitatively agree with the experimental ones.

  19. 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...

  20. International dynamic asset allocation and return predictability

    NARCIS (Netherlands)

    Basu, D.; Oomen, R.; Stremme, A.

    2010-01-01

    The presence of time varying investment opportunity sets has been documented in the context of international asset allocation, and the economic value associated with these is a topic of lively debate in the academic literature. This paper constructs simple, real-time dynamic international asset allo

  1. Bow and catapult internal dynamics

    CERN Document Server

    Denny, M

    2003-01-01

    A simple model of bow and arrow dynamics is presented, which makes clear the physical principles, and reproduces the features obtained via more detailed, but less accessible calculations. We apply this instructive model to determine the efficiency of bows and of torsion-spring catapults.

  2. Bow and catapult internal dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Denny, Mark [4665 Amblewood Drive, Victoria, BC V8Y 1C1 (Canada)

    2003-07-01

    A simple model of bow and arrow dynamics is presented, which makes clear the physical principles, and reproduces the features obtained via more detailed, but less accessible calculations. We apply this instructive model to determine the efficiency of bows and of torsion-spring catapults.

  3. Anomalous excited-state dynamics of lucifer yellow CH in solvents of high polarity: evidence for an intramolecular proton transfer.

    Science.gov (United States)

    Panda, Debashis; Mishra, Padmaja P; Khatua, Saumyakanti; Koner, Apurba L; Sunoj, Raghavan B; Datta, Anindya

    2006-05-04

    The photophysics of the fluorescent probe Lucifer yellow CH has been investigated using fluorescence spectroscopic and computational techniques. The nonradiative rate is found to pass through a minimum in solvents of intermediate empirical polarity. This apparently anomalous behavior is rationalized by considering the possibility of predominance of different kinds of nonradiative processes, viz. intersystem crossing (ISC) and excited-state proton transfer (ESPT), in solvents of low and high empirical polarity, respectively. The feasibility of the proton transfer is examined by the structure determined by the density functional theory (DFT) calculations. The predicted energy levels based on the time-dependent density functional theory (TD-DFT) method in the gas phase identifies the energy gap between the S(1) and nearest triplet state to be close enough to facilitate ISC. Photophysical investigation in solvent mixtures and in deuterated solvents clearly indicates the predominance of the solvent-mediated intramolecular proton transfer in the excited state of the fluorophore in protic solvents.

  4. Intramolecular structure and dynamics of mequinol and guaiacol in the gas phase: Rotationally resolved electronic spectra of their S{sub 1} states

    Energy Technology Data Exchange (ETDEWEB)

    Ruiz-Santoyo, José Arturo; Rodríguez-Matus, Marcela; Álvarez-Valtierra, Leonardo, E-mail: leoav@fisica.ugto.mx, E-mail: gmerino@mda.cinvestav.mx [División de Ciencias e Ingenierías, Universidad de Guanajuato-Campus León, León, Guanajuato 37150 (Mexico); Cabellos, José Luis; Merino, Gabriel, E-mail: leoav@fisica.ugto.mx, E-mail: gmerino@mda.cinvestav.mx [Departamento de Física Aplicada, Centro de Investigación y de Estudios Avanzados Unidad Mérida, Mérida, Yucatán 97310 (Mexico); Yi, John T. [Department of Chemistry, Winston-Salem State University, Winston-Salem, North Carolina 27110 (United States); Pratt, David W. [Department of Chemistry, University of Vermont, Burlington, Vermont 05405 (United States); Schmitt, Michael [Physikalische Chemie, Heinrich-Heine-Universität, Düsseldorf, Deutschland 40204 (Germany)

    2015-09-07

    The molecular structures of guaiacol (2-methoxyphenol) and mequinol (4-methoxyphenol) have been studied using high resolution electronic spectroscopy in a molecular beam and contrasted with ab initio computations. Mequinol exhibits two low frequency bands that have been assigned to electronic origins of two possible conformers of the molecule, trans and cis. Guaiacol also shows low frequency bands, but in this case, the bands have been assigned to the electronic origin and vibrational modes of a single conformer of the isolated molecule. A detailed study of these bands indicates that guaiacol has a vibrationally averaged planar structure in the ground state, but it is distorted along both in-plane and out-of-plane coordinates in the first electronically excited state. An intramolecular hydrogen bond involving the adjacent   –OH and   –OCH{sub 3} groups plays a major role in these dynamics.

  5. Fast internal dynamics in alcohol dehydrogenase

    Energy Technology Data Exchange (ETDEWEB)

    Monkenbusch, M.; Stadler, A., E-mail: a.stadler@fz-juelich.de; Biehl, R.; Richter, D. [Jülich Centre for Neutron Science JCNS and Institute for Complex Systems ICS, Forschungszentrum Jülich GmbH, 52425 Jülich (Germany); Ollivier, J. [Institut Laue-Langevin, CS 20156, 38042 Grenoble (France); Zamponi, M. [Jülich Centre for Neutron Science JCNS, Forschungszentrum Jülich GmbH, Outstation at MLZ, Lichtenbergstraße 1, 85747 Garching (Germany)

    2015-08-21

    Large-scale domain motions in alcohol dehydrogenase (ADH) have been observed previously by neutron spin-echo spectroscopy (NSE). We have extended the investigation on the dynamics of ADH in solution by using high-resolution neutron time-of-flight (TOF) and neutron backscattering (BS) spectroscopy in the incoherent scattering range. The observed hydrogen dynamics were interpreted in terms of three mobility classes, which allowed a simultaneous description of the measured TOF and BS spectra. In addition to the slow global protein diffusion and domain motions observed by NSE, a fast internal process could be identified. Around one third of the protons in ADH participate in the fast localized diffusive motion. The diffusion coefficient of the fast internal motions is around two third of the value of the surrounding D{sub 2}O solvent. It is tempting to associate the fast internal process with solvent exposed amino acid residues with dangling side chains.

  6. Fast internal dynamics in alcohol dehydrogenase

    Science.gov (United States)

    Monkenbusch, M.; Stadler, A.; Biehl, R.; Ollivier, J.; Zamponi, M.; Richter, D.

    2015-08-01

    Large-scale domain motions in alcohol dehydrogenase (ADH) have been observed previously by neutron spin-echo spectroscopy (NSE). We have extended the investigation on the dynamics of ADH in solution by using high-resolution neutron time-of-flight (TOF) and neutron backscattering (BS) spectroscopy in the incoherent scattering range. The observed hydrogen dynamics were interpreted in terms of three mobility classes, which allowed a simultaneous description of the measured TOF and BS spectra. In addition to the slow global protein diffusion and domain motions observed by NSE, a fast internal process could be identified. Around one third of the protons in ADH participate in the fast localized diffusive motion. The diffusion coefficient of the fast internal motions is around two third of the value of the surrounding D2O solvent. It is tempting to associate the fast internal process with solvent exposed amino acid residues with dangling side chains.

  7. 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.

  8. High resolution photoelectron spectroscopy and femtosecond intramolecular dynamics of H[sub 2]CCO[sup +] and D[sub 2]CCO[sup +

    Energy Technology Data Exchange (ETDEWEB)

    Niu, B.; Bai, Y.; Shirley, D.A. (Department of Chemistry, The University of California at Berkeley, Chemical Science Division, Lawrence Berkeley Laboratory, One Cyclotron Road, Berkeley, California 94720 (United States))

    1993-08-15

    High resolution helium I[alpha] (584 A) photoelectron spectra of H[sub 2]CCO and D[sub 2]CCO are reported. The present spectra of the ground states of ketene cations show more vibrational fine structure than previously reported. The adiabatic ionization energies (AIEs) of the cations' first, second, and fifth excited states are determined unambiguously. The doubletlike fine structures present in the first excited states of ketene cations imply the excitation of a soft'' mode that was not observed before. It was assigned to the [nu][sub 5] mode, which is characterized by the CH[sub 2] (CD[sub 2]) group out-of-plane wagging motion. The complexity of the photoelectron spectra obtained for the ionic first excited states is attributed to the possible dissociation and predissociation of this state. Strong isotope effects are observed in the vibronic (vibrational) couplings in most of the ionic states. Vibrational autocorrelation functions are calculated from the high-resolution photoelectron spectra for four of the six ionic states observed. The dynamics of the ground states of the cations are characterized by a wave packet oscillating with small amplitude around the minimum of the upper potential energy surfaces (PES). The decay dynamics of the ionic first and fifth excited states of ketene are characterized by ultrafast intramolecular processes such as dissociation and predissociation.

  9. Molecular crowding causes narrowing of population heterogeneity and restricts internal dynamics in a protein

    Science.gov (United States)

    Mondal, Samsuzzoha; Kallianpur, Mamata V.; Udgaonkar, Jayant B.; Krishnamoorthy, G.

    2016-03-01

    Macromolecular crowding is a distinguishing property of intracellular media. Knowledge on the structure and dynamics of a protein in a crowded environment is essential for a complete understanding of its function. Reduction in intermolecular space could cause structural and functional alterations. Here, we have studied a model protein barstar to see how polyethylene glycol (PEG)-induced crowding affects its various structural states (native, unfolded and molten-globule-like) with different extents of change in conformational heterogeneity. Intramolecular distances and distance distributions were determined by time-resolved Förster resonance energy transfer from Trp53 to several acceptor sites by analysis of fluorescence decay kinetics using the Maximum Entropy Method. We observed PEG-induced narrowing of population distributions along with shifting of populations towards more compact states. Structural compactness also resulted in the slowing down of internal dynamics of the protein as revealed by fluorescence anisotropy decay kinetics of the fluorophore IAEDANS attached at several sites.

  10. Nuclear quantum effect on intramolecular hydrogen bond of hydrogen maleate anion: An ab initio path integral molecular dynamics study

    Science.gov (United States)

    Kawashima, Yukio; Tachikawa, Masanori

    2013-05-01

    Ab initio path integral molecular dynamics simulation was performed to understand the nuclear quantum effect on the hydrogen bond of hydrogen malonate anion. Static calculation predicted the proton transfer barrier as 0.12 kcal/mol. Conventional ab initio molecular dynamics simulation at 300 K found proton distribution with a double peak on the proton transfer coordinate. Inclusion of thermal effect alone elongates the hydrogen bond length, which increases the barrier height. Inclusion of nuclear quantum effect washes out this barrier, and distributes a single broad peak in the center. H/D isotope effect on the proton transfer is also discussed.

  11. 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.

  12. 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 ...

  13. 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 rel...

  14. Visualizing the non-equilibrium dynamics of photoinduced intramolecular electron transfer with femtosecond X-ray pulses

    DEFF Research Database (Denmark)

    Canton, Sophie E.; Kjær, Kasper S.; Vankó, György;

    2015-01-01

    spectroscopy with ultrafast X-ray emission spectroscopy and diffuse X-ray scattering at the SACLA facility to track the non-equilibrated electronic and structural dynamics within a bimetallic donor–acceptor complex that contains an optically dark centre. Exploiting the 100-fold increase in temporal resolution...... states is a key mechanistic feature. The present study demonstrates the extensive potential of femtosecond X-ray techniques as diagnostics of non-adiabatic electron transfer processes in synthetic and biological systems, and some directions for future studies, are outlined....

  15. Visualizing the non-equilibrium dynamics of photoinduced intramolecular electron transfer with femtosecond X-ray pulses

    DEFF Research Database (Denmark)

    Canton, Sophie E.; Kjær, Kasper S.; Vankó, György;

    2015-01-01

    Ultrafast photoinduced electron transfer preceding energy equilibration still poses many experimental and conceptual challenges to the optimization of photoconversion since an atomic-scale description has so far been beyond reach. Here we combine femtosecond transient optical absorption...... spectroscopy with ultrafast X-ray emission spectroscopy and diffuse X-ray scattering at the SACLA facility to track the non-equilibrated electronic and structural dynamics within a bimetallic donor–acceptor complex that contains an optically dark centre. Exploiting the 100-fold increase in temporal resolution...

  16. Slow internal protein dynamics in solution

    Science.gov (United States)

    Biehl, R.; Richter, D.

    2014-12-01

    Large-scale domain dynamics in proteins are found when flexible linkers or hinges connect domains. The related conformational changes are often related to the function of the protein, for example by arranging the active center after substrate binding or allowing transport and release of products. The adaptation of a specific active structure is referred to as ‘induced fit’ and is challenged by models such as ‘conformational sampling’. Newer models about protein function include some flexibility within the protein structure or even internal dynamics of the protein. As larger domains contribute to the configurational changes, the timescale of the involved motions is slowed down. The role of slow domain dynamics is being increasingly recognized as essential to understanding the function of proteins. Neutron spin echo spectroscopy (NSE) is a technique that is able to access the related timescales from 0.1 up to several hundred nanoseconds and simultaneously covers the length scale relevant for protein domain movements of several nanometers distance between domains. Here we focus on these large-scale domain fluctuations and show how the structure and dynamics of proteins can be assessed by small-angle neutron scattering and NSE.

  17. Regularities in the dynamics and development of the International System

    CERN Document Server

    Piepers, Ingo

    2014-01-01

    A finite-time singularity accompanied by log-periodic oscillations shaped the war dynamics and development of the International System during the period 1495 - 1945. The identification of this singularity provides us with a perspective to penetrate and decode the dynamics of the International System. Various regularities in the dynamics of the International System can be identified. These regularities are remarkably consistent, and can be attributed to the connectivity and the growth of connectivity of the International System.

  18. Dynamical Properties of Internal Shocks Revisited

    CERN Document Server

    Pe'er, Asaf; Casella, Piergiorgio

    2016-01-01

    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 lightcurve 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 collision between arbitrarily hot plasma shells, moving at arbitrary speeds. We provide simple analytical expressions valid for both the ultra-relativistic 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...

  19. Dynamics of exosome internalization and trafficking.

    Science.gov (United States)

    Tian, Tian; Zhu, Yan-Liang; Hu, Fei-Hu; Wang, Yuan-Yuan; Huang, Ning-Ping; Xiao, Zhong-Dang

    2013-07-01

    Cells release exosomes into extracellular medium. Although the important roles of exosomes in many physiological and pathological processes are being revealed, the mechanism of exosome-cell interaction remains unclear. In this article, employing real-time fluorescence microscopy, the motion of exosomes on the plasma membrane or in the cytoplasm of recipient PC12 cells was observed directly. In addition, several motion modes of exosomes were revealed by single particle tracking (SPT). The changes between motion modes were also detected, presenting the dynamic courses of exosome attachment onto plasma membrane and exosome uptake. Octadecyl rhodamine B chloride (R18) was found to be useful to distinguish endocytosis from fusion during exosome uptake. Colocalization with organelle markers showed exosomes were sorted to acidic vesicles after internalization. The results provide new sight into the exosome-cell interaction mode and the intercellular trafficking of exosomes. This study will help to understand the roles of exosomes at cell level.

  20. Interactions in dendronized polymers: intramolecular dominates intermolecular.

    Science.gov (United States)

    Córdova-Mateo, Esther; Bertran, Oscar; Zhang, Baozhong; Vlassopoulos, Dimitris; Pasquino, Rossana; Schlüter, A Dieter; Kröger, Martin; Alemán, Carlos

    2014-02-21

    In an attempt to relate atomistic information to the rheological response of a large dendritic object, interand intramolecular hydrogen bonds and p,p-interactions have been characterized in a dendronized polymer (DP) that consists of a polymethylmethacrylate backbone with tree-like branches of generation four (PG4) and contains both amide and aromatic groups. Extensive atomistic molecular dynamics simulations have been carried out on (i) an isolated PG4 chain and (ii) ten dimers formed by two PG4 chains associated with different degrees of interpenetration. Results indicate that the amount of nitrogen atoms involved in hydrogen bonding is ~11% while ~15% of aromatic groups participate in p,pinteractions. Furthermore, in both cases intramolecular interactions clearly dominate over intermolecular ones, while exhibiting markedly different behaviors. Specifically, the amount of intramolecular hydrogen bonds increases when the interpenetration of the two chains decreases, whereas intramolecular p,pinteractions remain practically insensitive to the amount of interpenetration. In contrast, the strength of the corresponding two types of intermolecular interactions decreases with interpenetration. Although the influence of complexation on the density and cross-sectional radius is relatively small, interpenetration affects significantly the molecular length of the DP. These results support the idea of treating DPs as long colloidal molecules.

  1. Car-Parrinello and path integral molecular dynamics study of the intramolecular hydrogen bond in the novel class of anionic H-chelates: 6-Nitro-2,3-dipyrrol-2-ylquinoxaline anion

    Science.gov (United States)

    Durlak, Piotr; Latajka, Zdzisław

    2009-10-01

    Theoretical studies of the structure and proton motion in the intramolecular N-H⋯N hydrogen bond in 6-nitro-2,3-dipyrrol-2-ylquinoxaline anion were carried out at the DFT, MP2 and molecular dynamics levels. Geometry optimization at the 6-311++G(2d,2p) level demonstrate existence of two tautomers on the potential energy surface. The difference in energy between both tautomers is equals 1.62 (1.42) kcal/mol. Dynamics of proton motion in the N-H⋯N hydrogen bond was investigated in vacuum at 233 K using Car-Parrinello and path integral molecular dynamics. Very large delocalization of bridging proton is noted especially in path integral simulation. DFT calculated the coupling constant across the hydrogen bond equals 16.5 Hz is in good agreement with experimental value.

  2. Nonlinear dynamics of hydrostatic internal gravity waves

    Energy Technology Data Exchange (ETDEWEB)

    Stechmann, Samuel N.; Majda, Andrew J. [New York University, Courant Institute of Mathematical Sciences, NY (United States); Khouider, Boualem [University of Victoria, Department of Mathematics and Statistics, Victoria, BC (Canada)

    2008-11-15

    Stratified hydrostatic fluids have linear internal gravity waves with different phase speeds and vertical profiles. Here a simplified set of partial differential equations (PDE) is derived to represent the nonlinear dynamics of waves with different vertical profiles. The equations are derived by projecting the full nonlinear equations onto the vertical modes of two gravity waves, and the resulting equations are thus referred to here as the two-mode shallow water equations (2MSWE). A key aspect of the nonlinearities of the 2MSWE is that they allow for interactions between a background wind shear and propagating waves. This is important in the tropical atmosphere where horizontally propagating gravity waves interact together with wind shear and have source terms due to convection. It is shown here that the 2MSWE have nonlinear internal bore solutions, and the behavior of the nonlinear waves is investigated for different background wind shears. When a background shear is included, there is an asymmetry between the east- and westward propagating waves. This could be an important effect for the large-scale organization of tropical convection, since the convection is often not isotropic but organized on large scales by waves. An idealized illustration of this asymmetry is given for a background shear from the westerly wind burst phase of the Madden-Julian oscillation; the potential for organized convection is increased to the west of the existing convection by the propagating nonlinear gravity waves, which agrees qualitatively with actual observations. The ideas here should be useful for other physical applications as well. Moreover, the 2MSWE have several interesting mathematical properties: they are a system of nonconservative PDE with a conserved energy, they are conditionally hyperbolic, and they are neither genuinely nonlinear nor linearly degenerate over all of state space. Theory and numerics are developed to illustrate these features, and these features are

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

    Science.gov (United States)

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

    2007-05-01

    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 pi flips and oscillation motions for phenylene rings. The associated time scales are broadly distributed with mean activation energies equal to 0.41 and 0.21eV , respectively. Finally, a comparative study with the literature shows that the dielectric and mechanical gamma 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. Intramolecular carbonickelation of alkenes

    Directory of Open Access Journals (Sweden)

    Rudy Lhermet

    2013-04-01

    Full Text Available The efficiency of the intramolecular carbonickelation of substituted allylic ethers and amines has been studied to evaluate the influence of the groups borne by the double bond on this cyclization. The results show that when this reaction takes place, it affords only the 5-exo-trig cyclization products, viz. dihydrobenzofurans or indoles. Depending on the tethered heteroatom (O or N, the outcome of the cyclization differs. While allylic ethers are relatively poor substrates that undergo a side elimination and need an intracyclic double bond to proceed, allylic amines react well and afford indoline and indole derivatives. Finally, the synthesis of the trinuclear ACE core of a morphine-like skeleton was achieved by using NiBr2bipy catalysis.

  5. Rotation and internal dynamics of terrestrial planets

    Science.gov (United States)

    Dehant, V.

    2009-04-01

    In the last decades, several missions and observations have brought new insight on the inner structure of the terrestrial planets. This information is a big challenge for the planet interior models; these data are also our best chance to improve our knowledge of the interior. Data obtained through new space missions are the basis of the future progress in this field. Classically, as done for the Earth, the interior models are constrained through seismic data provided from an extended network of seismometers. However, for planets, in the absence of such a network, gravitation and rotation studies are the most efficient ways to learn about the interior of the planets. Practically, our study is based on the analysis of the precise orbits of spacecrafts around the planets and on the positions of landers. Experiments on the planet Mars and Mercury will allow us to answer some of the most debated questions of the moment. On Mars, we plan in particular for the LaRa (Lander radioscience) instrument to be part of the Humboldt Payload (on the fixed platform lander) of the ExoMars ESA mission. LaRa is a coherent transponder using one uplink and one downlink in X-band. LaRa will measure the variation of Mars' rotation rate (related to the length-of-day) and the orientation of Mars' rotation axis in space (precession and nutations), by measuring Doppler shifts resulting from the motion of Mars relative to the Earth, through monitoring a radio signal between the ExoMars lander and the tracking stations from ESA (ESTRACK stations) and NASA (the Deep Space Network, DSN) on Earth. The primary objective of LaRa is a precise measurement of precession, nutations, and length-of-day. Comparing the data with theoretical modeling allows inferring knowledge on Mars' interior and on the global circulation in its atmosphere. Precession and nutations are induced by the well-known gravitational forcing of the Sun on Mars. Nutations depend on the internal properties of Mars, in particular on

  6. Solvent control of intramolecular proton transfer

    DEFF Research Database (Denmark)

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

    2017-01-01

    The solvent dependent excited state dynamics of 4-hydroxy-3-(piperidin-1-ylmethyl)-1-naphthaldehyde (compound 2), a candidate for a molecular switch based on intramolecular proton transfer, was investigated by ultrafast spectroscopy and quantum-chemical calculations. In acetonitrile a mixture...... 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....... In addition we observe the appearance of a long living species with a rate of 1/(330 ps) which returns to the original ground state on time scales beyond 2 ns and which is attributed to the triplet state. In toluene the enol form is the only observed ground state tautomer, but no light induced proton transfer...

  7. 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.

  8. 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.

  9. DYNAMIC DESIGN OF INTERNAL COMBUSTION ENGINE BLOCK STRUCTURE

    Institute of Scientific and Technical Information of China (English)

    1998-01-01

    Several main steps of internal combustion engine block structure dynamic design,such as model set-up,structure dynamic response analysis,optimizing design and vibration and noise control,are discussed for the type of EQ6100 gasoline engine block.

  10. 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.

  11. 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...

  12. Enhancing the output current of a CdTe solar cell via a CN-free hydrocarbon luminescent down-shifting fluorophore with intramolecular energy transfer and restricted internal rotation characteristics.

    Science.gov (United States)

    Li, Yilin; Olsen, Joseph; Dong, Wen-Ji

    2015-04-01

    A CN-free hydrocarbon fluorophore (Perylene-TPE) was synthesized as a new luminescent down-shifting (LDS) material. Its photophysical properties in both the solution state and the solid state were studied. The unity fluorescence quantum yield of Perylene-TPE observed in its solid state is considered to be from the characteristics of intramolecular energy transfer (IET) and restricted internal rotation (RIR). This is supported by the results from theoretical calculations and spectroscopic measurements. For the photovoltaic application of Perylene-TPE, a theoretical modeling study suggests that using the LDS film of Perylene-TPE may increase the output short circuit current density (Jsc) of a CdTe solar cell by 2.95%, enhance the spectral response of a CdTe solar cell at 400 nm by 41%, and shift the incident solar photon distribution from short-wavelength (500 nm). Experimentally, placing a LDS film of Perylene-TPE on a CdTe solar cell can enhance its output Jsc by as high as 3.30 ± 0.31%, which is comparable to the current commercially available LDS material – Y083 (3.28% ± 0.37%).

  13. Rotation dynamics with & without Internal Transport Barriers

    Science.gov (United States)

    Dif-Pradalier, Guilhem; Diamond, Patrick H.; Chang, C. S.; Ku, S.; Sarazin, Y.; Grandgirard, V.; Abiteboul, J.; Garbet, X.; Ghendrih, Ph.; Strugarek, A.

    2009-11-01

    We investigate the dynamics of both poloidal and toroidal flows in the presence (or absence) of a reversed safety factor profile through a scan in the incoming heat power applied to the plasma. Doing so, it incidentally also addresses the question of a power threshold for a self-consistent ITB formation in gyrokinetic modeling. As a prime candidate to drive the system away from its neoclassical prediction, we recently showed evidence of turbulence-generated poloidal rotation, consistently with earlier theories. Accurate calculation of the radial electric field is central. Accordingly, description of the mean profile dynamics, as done in full--f flux-driven models is shown to take on a very prominent role. The study is performed using both the Gysela and Xgc--1 gyrokinetic codes with Enhanced Reverse Shear (ERS)-like parameters.

  14. Second International Colloquium on Dynamical Systems

    CERN Document Server

    Seade, José; Verjovski, Alberto

    1988-01-01

    The objective of the meeting was to have together leading specialists in the field of Holomorphic Dynamical Systems in order to present their current reseach in the field. The scope was to cover iteration theory of holomorphic mappings (i.e. rational maps), holomorphic differential equations and foliations. Many of the conferences and articles included in the volume contain open problems of current interest. The volume contains only research articles.

  15. Dynamic model for the internal combustion engine

    Energy Technology Data Exchange (ETDEWEB)

    Rizzoni, G.

    1986-01-01

    Over the last decade there has been increasing interest in the application of control theory to passenger vehicles: stringent governmental regulations constraining fuel consumption and exhaust emissions have required a shift to integrated electronics controls. Unfortunately, the lack of robust global models for the dynamics of the IC engine has limited the application of the tools of control theory in this areas. This dissertation is devoted to the formulation of a robust model for the dynamics of the IC engine. The engine is viewed as a system with inputs given by cylinder pressure and net engine torque, and output corresponding to crankshaft angular acceleration. The model is well suited to closed loop engine and transmission control applications. The deterministic model provides a powerful tool for estimating average and instantaneous net engine torque based on a noncontacting measurement of crankshaft acceleration. The stochastic model explains cyclic pressure variations by an additive Gaussian WSS vector noise process. Further, it demonstrates that by means of a suitable linear transformation-invariant with load and RPM-, the noise process may be expressed in terms of a three-dimensional uncorrelated vector random process.

  16. 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.

  17. 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.

  18. The intramolecular electron transfer between copper sites of nitrite reductase

    DEFF Research Database (Denmark)

    Farver, O; Eady, R R; Abraham, Z H

    1998-01-01

    The intramolecular electron transfer (ET) between the type 1 Cu(I) and the type 2 Cu(II) sites of Alcaligenes xylosoxidans dissimilatory nitrite reductase (AxNiR) has been studied in order to compare it with the analogous process taking place in ascorbate oxidase (AO). This internal process...

  19. 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

    Energy Technology Data Exchange (ETDEWEB)

    Kojima, H.; Yamada, A.; Okazaki, S., E-mail: okazaki@apchem.nagoya-u.ac.jp [Department of Applied Chemistry, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8603 (Japan)

    2015-05-07

    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.

  20. Dynamic Transfer Schemes and Stability of International Climate Coalitions

    NARCIS (Netherlands)

    Nagashima, M.N.; Dellink, R.B.; Ierland, van E.C.

    2006-01-01

    This paper examines the formation and stability of coalitions in international climate agreements with a combined game-theoretic and integrated assessment model. The empirical model comprises twelve regions and investigates partial coalition formation in a one-shot cartel game. We argue that a dynam

  1. Structure and Dynamics of a Trinuclear Gadolinium(III) Complex: The Effect of Intramolecular Electron Spin Relaxation on Its Proton Relaxivity(1).

    Science.gov (United States)

    Tóth É, Éva; Helm, Lothar; Merbach, André E.; Hedinger, Roman; Hegetschweiler, Kaspar; Jánossy, András

    1998-08-10

    The trinuclear [Gd(3)(H(-)(3)taci)(2)(H(2)O)(6)](3+) complex has been characterized in aqueous solution as a model compound from the point of view of MRI: the parameters that affect proton relaxivity have been determined in a combined variable temperature, pressure, and multiple-field (17)O NMR, EPR, and NMRD study. The solution structure of the complex was found to be the same as in solid state: the total coordination number of the lanthanide(III) ion is 8 with two inner-sphere water molecules. EPR measurements proved a strong intramolecular dipole-dipole interaction between Gd(III) electron spins. This mechanism dominates electron spin relaxation at high magnetic fields (B > 5 T). Its proportion to the overall relaxation decreases with decreasing magnetic field and becomes a minor term at fields used in MRI. Consequently, it cannot increase the electronic relaxation rates to such an extent that they limit proton relaxivity. [Gd(3)(H(-)(3)taci)(2)(H(2)O)(6)](3+) undergoes a relatively slow water exchange (k(ex)(298) = (1.1 +/- 0.2) x 10(7) s(-1)) compared to the Gd(III) aqua ion, while the mechanism is much more associatively activated as shown by the activation volume (DeltaV () = (-12.7 +/- 1.5) cm(3) mol(-)(1)). The lower exchange rate, as compared to [Gd(H(2)O)(8)](3+) and [Gd(PDTA)(H(2)O)(2)](-), can be explained with the higher rigidity of the [Gd(3)(H(-)(3)taci)(2)(H(2)O)(6)](3+) which considerably slows down the transition from the eight-coordinate reactant to the nine-coordinate transition state. The unexpectedly low rotational correlation time of the complex is interpreted in terms of a spherical structure with a large hydrophobic surface avoiding the formation of a substantial hydration sphere around [Gd(3)(H(-)(3)taci)(2)(H(2)O)(6)](3+).

  2. 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...

  3. On the internal dynamics of starless cores: stability of starless cores with internal motions and collapse dynamics

    CERN Document Server

    Seo, Young Min; Shirley, Yancy L

    2013-01-01

    In order to understand the collapse dynamics of observed low-mass starless cores, we revise the conventional stability condition of hydrostatic Bonnor-Ebert spheres to take internal motions into account. Because observed starless cores resemble Bonnor-Ebert density structures, the stability and dynamics of the starless cores are frequently analyzed by comparing to the conventional stability condition of a hydrostatic Bonnor-Ebert sphere. However, starless cores are not hydrostatic but have observed internal motions. In this study, we take gaseous spheres with a homologous internal velocity field and derive stability conditions of the spheres utilizing a virial analysis. We propose two limiting models of spontaneous gravitational collapse: the collapse of critical Bonnor-Ebert spheres and uniform density spheres. The collapse of these two limiting models are intended to provide the lower and the upper limits, respectively, of the infall speeds for a given density structure. The results of our study suggest tha...

  4. Dynamics of ultrafast intramolecular charge transfer with 1-tert-butyl-6-cyano-1,2,3,4-tetrahydroquinoline (NTC6) in n-hexane and acetonitrile.

    Science.gov (United States)

    Druzhinin, Sergey I; Kovalenko, Sergey A; Senyushkina, Tamara; Zachariasse, Klaas A

    2007-12-20

    The intramolecular charge transfer (ICT) reaction of 1-tert-butyl-6-cyano-1,2,3,4-tetrahydroquinoline (NTC6) in n-hexane and acetonitrile (MeCN) is investigated by picosecond fluorescence experiments as a function of temperature and by femtosecond transient absorption measurements at room temperature. NTC6 in n-hexane is dual fluorescent from a locally excited (LE) and an ICT state, with a quantum yield ratio Phi'(ICT)/Phi(LE) of 0.35 at +25 degrees C and 0.67 at -95 degrees C, whereas in MeCN mainly an ICT emission is observed. From the temperature dependence of Phi'(ICT)/Phi(LE) for NTC6 in n-hexane, an LE/ICT enthalpy difference DeltaH of -2.4 kJ/mol is determined. For comparison, 1-isopropyl-6-cyano-1,2,3,4-tetrahydroquinoline (NIC6) is also investigated. This molecule does not undergo an ICT reaction, because of its larger energy gap DeltaE(S1,S2). From the molar absorption coefficient epsilonmax of NTC6 as compared with other aminobenzonitriles, a ground-state amino twist angle theta of approximately 22 degrees is deduced. The increase of epsilonmax between n-hexane and MeCN indicates that theta decreases when the solvent polarity becomes larger. Whereas single-exponential LE fluorescence decays are obtained for NIC6 in n-hexane and MeCN, the LE and ICT decays of NTC6 in these solvents are double exponential. For NTC6 in n-hexane at -95 degrees C, with a shortest decay time of 20 ps, the forward (ka=2.5x10(10) s(-1)) and backward (kd=2.7x10(10) s(-1)) rate constants for the LEICT reaction are determined from the time-resolved LE and ICT fluorescence spectra. For NTC6 in n-hexane and MeCN, the excited-state absorption (ESA) spectrum at 200 fs after excitation is similar to the LE(ESA) spectra of NIC6 and 4-(dimethylamino)benzonitrile (DMABN), showing that LE is the initially excited state for NTC6. These results indicate that the LE states of NTC6, NIC6, and DMABN have a comparable molecular structure. The ICT(ESA) spectrum of NTC6 in n-hexane and Me

  5. Modeling the dynamics of intense internal waves on the shelf

    Science.gov (United States)

    Talipova, T. G.; Pelinovsky, E. N.; Kurkin, A. A.; Kurkina, O. E.

    2014-11-01

    The transformation of the internal wave packet during its propagation over the shelf of Portugal was studied in the international experiment EU MAST II MORENA in 1994. This paper presents the results of modeling of the dynamics of this packet under hydrological conditions along the pathway of its propagation. The modeling was performed on the basis of the generalized Gardner-Ostrovskii equation, including inhomogeneous hydrological conditions, rotation of the Earth, and dissipation in the bottom boundary layer. We also discuss the results of the comparison of the observed and simulated forms and phases of individual waves in a packet at reference points.

  6. A Rational Approach to Ring Flexibility in Internal Coordinate Dynamics

    CERN Document Server

    Mazur, A K

    1998-01-01

    Internal coordinate molecular dynamics (ICMD) is an efficient method for studying biopolymers, but it is readily applicable only to molecules with tree topologies, that is with no internal flexible rings. Common examples violating this condition are prolines and loops closed by S-S bridges in proteins. The most important such case, however, is nucleic acids because the flexibility of the furanose rings always plays an essential role in conformational transitions both in DNA and RNA. There are a few long-known theoretical approaches to this problem, but, in practice, rings with fixed bond lengths are closed by adding appropriate harmonic distance restraints, which is not always acceptable especially in dynamics. This paper tries to overcome this handicap of ICMD and proposes a rational strategy which results in practical numerical algorithms. It gives a unified analytical treatment which shows that this problem is very close to the difficulties encountered by the method of constraints in Cartesian coordinate d...

  7. Intramolecular Charge Transfer in Arylpyrazolines

    Institute of Scientific and Technical Information of China (English)

    WANG Ming-Liang; LIU Ju-Zheng; XU Chun-Xiang

    2006-01-01

    @@ Arylpyrazoline microparticles dispersed in water are synthesized and their absorption spectra are compared with those in solution. It is found that the absorbance of pyrazoline group in solution of 5-aryl arylpyrazoline is far greater than that in solution of arylpyrazolines with no 5-aryl group. This hyperchromic effect is intensified in 5-aryl arylpyrazoline microparticles. It is indicated that intramolecular charge transfer exists between pyrazoline group and 5-aryl group and this kind of interaction is increased in their microparticles.

  8. A Car-Parrinello and path integral molecular dynamics study of the intramolecular lithium bond in the lithium 2-pyridyl-N-oxide acetate

    Science.gov (United States)

    Durlak, Piotr; Latajka, Zdzisław; Berski, Sławomir

    2009-07-01

    Lithium bonding in lithium 2-pyridyl-N-oxide acetate has been investigated using classic Car-Parrinello molecular dynamics (CPMD) and the path integral approach [path integrals molecular dynamics (PIMD)]. The simulations have been performed in 300 K. Structures, energies, and lithium trajectories have been determined. The CPMD results show that the lithium atom is generally equidistant between heavy atoms in the (O⋯Li⋯O) bridge. Applying quantum effects through the PIMD leads to similar conclusion. The theoretical lithium 2-pyridyl-N-oxide acetate infrared spectrum has also been determined using the CPMD calculations. This shows very good agreement with available experimental results and reproduces well the broad low-frequency band observed experimentally. In order to gain deeper understanding of the nature of the lithium bonding topological analysis of the electron localization function has been applied.

  9. 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.

  10. 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.

  11. 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.

  12. Ultrafast Non-Förster Intramolecular Donor-Acceptor Excitation Energy Transfer.

    Science.gov (United States)

    Athanasopoulos, Stavros; Alfonso Hernandez, Laura; Beljonne, David; Fernandez-Alberti, Sebastian; Tretiak, Sergei

    2017-04-06

    Ultrafast intramolecular electronic energy transfer in a conjugated donor-acceptor system is simulated using nonadiabatic excited-state molecular dynamics. After initial site-selective photoexcitation of the donor, transition density localization is monitored throughout the S2 → S1 internal conversion process, revealing an efficient unidirectional donor → acceptor energy-transfer process. Detailed analysis of the excited-state trajectories uncovers several salient features of the energy-transfer dynamics. While a weak temperature dependence is observed during the entire electronic energy relaxation, an ultrafast initially temperature-independent process allows the molecular system to approach the S2-S1 potential energy crossing seam within the first ten femtoseconds. Efficient energy transfer occurs in the absence of spectral overlap between the donor and acceptor units and is assisted by a transient delocalization phenomenon of the excited-state wave function acquiring Frenkel-exciton character at the moment of quantum transition.

  13. The dynamics of internal working surfaces in MHD jets

    CERN Document Server

    De Colle, Fabio; Esquivel, Alejandro

    2008-01-01

    The dynamical effects of magnetic fields in models of radiative, Herbig-Haro (HH) jets have been studied in a number of papers. For example, magnetized, radiative jets from variable sources have been studied with axisymmetric and 3D numerical simulations. In this paper, we present an analytic model describing the effect of a toroidal magnetic field on the internal working surfaces that result from a variability in the ejection velocity. We find that for parameters appropriate for HH jets the forces associated with the magnetic field dominate over the gas pressure force within the working surfaces. Depending on the ram pressure radial cross section of the jet, the magnetic field can produce a strong axial pinch, or, alternatively, a broadening of the internal working surfaces. We check the validity of the analytic model with axisymmetric numerical simulations of variable, magnetized jets.

  14. 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...

  15. 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.

  16. Tracing the Cluster Internal Dynamics with Member Galaxies

    OpenAIRE

    Biviano, Andrea

    2001-01-01

    The analysis of the spatial distribution and kinematics of galaxies in clusters allows one to determine the cluster internal dynamics. In this paper, I review the state of the art of this topic. In particular, I summarize what we have learned so far about galaxy orbits in clusters, and about the cluster mass distribution. I then compare four methods that have recently been used in the literature, by applying them to the same data-set. The results stress the importance of reducing systematic b...

  17. Internal character dictates transition dynamics between isolation and cohesive grouping

    Science.gov (United States)

    Manrique, Pedro D.; Hui, Pak Ming; Johnson, Neil F.

    2015-12-01

    We show that accounting for internal character among interacting heterogeneous entities generates rich transition behavior between isolation and cohesive dynamical grouping. Our analytical and numerical calculations reveal different critical points arising for different character-dependent grouping mechanisms. These critical points move in opposite directions as the population's diversity decreases. Our analytical theory may help explain why a particular class of universality is so common in the real world, despite the fundamental differences in the underlying entities. It also correctly predicts the nonmonotonic temporal variation in connectivity observed recently in one such system.

  18. Intramolecular fluorescence correlation spectroscopy in a feedback tracking microscope

    CERN Document Server

    McHale, Kevin

    2009-01-01

    We derive the statistics of the signals generated by shape fluctuations of large molecules studied by feedback tracking microscopy. We account for the influence of intramolecular dynamics on the response of the tracking system, and derive a general expression for the fluorescence autocorrelation function that applies when those dynamics are linear. We show that tracking provides enhanced sensitivity to translational diffusion, molecular size, heterogeneity and long time-scale decays in comparison to traditional fluorescence correlation spectroscopy. We demonstrate our approach by using a three-dimensional tracking microscope to study genomic $\\lambda$-phage DNA molecules with various fluorescence label configurations. We conclude with a discussion of related techniques, including computation of the relevant statistics for camera-based intramolecular correlation measurements.

  19. A new formalism for molecular dynamics in internal coordinates

    Science.gov (United States)

    Lee, Sang-Ho; Palmo, Kim; Krimm, Samuel

    2001-03-01

    Internal coordinate molecular dynamics (ICMD) has been used in the past in simulations for large molecules as an alternative way of increasing step size with a reduced operational dimension that is not achievable by MD in Cartesian coordinates. A new ICMD formalism for flexible molecular systems is presented, which is based on the spectroscopic B-matrix rather than the A-matrix of previous methods. The proposed formalism does not require an inversion of a large matrix as in the recursive formulations based on robot dynamics, and takes advantage of the sparsity of the B-matrix, ensuring computational efficiency for flexible molecules. Each molecule's external rotations about an arbitrary atom center, which may differ from its center of mass, are parameterized by the SU(2) Euler representation, giving singularity free parameterization. Although the formalism is based on the use of nonredundant generalized (internal and external) coordinates, an MD simulation in linearly dependent coordinates can be done by finding a transformation to a new set of independent coordinates. Based on the clear separability in the generalized coordinates between fast varying degrees of freedom and slowly varying ones, a multiple time step algorithm is introduced that avoids the previous nontrivial interaction distance classification. Also presented is a recursive method for computing nonzero A-matrix elements that is much easier to apply to a general molecular structure than the previous method.

  20. Dendrimer light-harvesting: intramolecular electrodynamics and mechanisms.

    Science.gov (United States)

    Andrews, David L; Bradshaw, David S; Jenkins, Robert D; Rodríguez, Justo

    2009-12-01

    In the development of highly efficient materials for harvesting solar energy, there is an increasing focus on purpose-built dendrimers and allied multi-chromophore systems. A proliferation of antenna chromophores is not the only factor determining the sought light-harvesting efficiency; the internal geometry and photophysics of these molecules are also crucially important. In particular, the mechanisms by means of which radiant energy is ultimately trapped depends on an intricate interplay of electronic, structural, energetic and symmetry properties. To better understand these processes a sound theoretical representation of the intramolecular electrodynamics is required. A suitable formalism, based on quantum electrodynamics, readily delivers physical insights into the necessary excitation channelling processes, and it affords a rigorous basis for modelling the intramolecular flow of energy.

  1. Solar neutrinos, helioseismology and the solar internal dynamics

    CERN Document Server

    Turck-Chieze, S

    2010-01-01

    Neutrinos are fundamental particles ubiquitous in the Universe. Their properties remain elusive despite more than 50 years of intense research activity. In this review 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 to 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 waves propagating in the Sun. This review reminds the historical steps, from the pioneering Homestake detection, the GALLEX- SAGE captures of the first pp neutrinos and emphasizes the importance of the Superkamiokande and SNO detectors to demonstrate that the solar-emitted electronic neutrinos are partially...

  2. 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......The article focuses on long-term development of technology-based international new ventures (INVs) and discusses aspects of managing such ventures once they are past the initial success and rapid internationalization and enter the stable development phase. The study builds on an in-depth process...... 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...

  3. Probing Internal Dynamics of two SMGs with OSIRIS

    Science.gov (United States)

    Menendez-Delmestre, K.; Blain, A. W.; Chapman, S. C.; Swinbank, A. M.; Smail, I.; Ivison, R. J.; Alexander, D. M.

    2005-12-01

    We used the OH-Suppresing Infrared Imaging Spectrograph (OSIRIS) on Keck II with laser AO to investigate the internal dynamics of two of the most luminous submillimeter galaxies (SMGs) at redshifts z 2-3: SMM J030227.73+000653.5 at z=1.408 and SMM J221804.42+002154.4 at z=2.517 (Chapman et al. 2005). Recent ultradeep Chandra X-ray results indicate that the majority of SMGs contain an actively fueled AGN (Alexander et al. 2005), as their hard X-ray emission is too powerful to be explained by the high-mass X-ray binaries associated with pure star formation. This AGN contributes a minor fraction to the total luminosity, but the potential modifies the observed spectra, complicating their interpretation in terms of excitation and metallicity. We expect the restframe optical light from this nuclear emission to be centrally concentrated, surrounded by a more extended emission from star-forming regions. With AO we attempt to resolve the separation between the nuclear and extended emission, to probe the AGN and the velocity field of the wider starburst. We aimed to map the two-dimensional spatial distribution of H-alpha line emission, using the appropriate narrow band filters Hn2 and Kn5 matched to our known redshifts using the coarsest OSIRIS plate scale (0.1-arcsec) to have the largest field of view and optimize the coverage of the luminous region of the galaxies. By measuring accurately both the velocity dispersion point-by-point and the physical extent of these high redshift galaxies, we can estimate their dynamical masses. This enables us to better understand their internal astrophysics, their fate in terms of the galaxies we observe today, and the links between properties of dark matter halos and the stellar systems that form within. We thank NASA, NSF and Sloan Foundation.

  4. The 7th International Workshop on Chiral Dynamics

    Science.gov (United States)

    The 7th International Workshop Chiral Dynamics: Theory and Experiment (CD12) took place at Jefferson Lab, Newport News, Virginia, USA, from August 6 to 10, 2012. Following in the tradition of this triennial series of Conferences, it attracted theorists and experimentalists, who were brought together to highlight the recent progress in the field of low energy QCD, and to discuss and explore the direction for future development. The conference consisted of plenary talks and three working groups. We would like to thank the working group organizers for their dedicated effort, namely: Goldstone Bosons: Mario Antonelli, Liping Gan, Jorge Portoles and Urs Wenger; Hadron Structure: Alessandro Bacchetta, Bastian Kubis, Kostas Orginos and Karl Slifer and Few Body Physics: Andreas Nogga, Assumpta Parreno, Michele Viviani and Henry Weller. We would like to express our special thanks to our co-organizers, Patricia Solvignon, Harald Griesshammer, Rocco Schiavilla, Dinko Pocanic, Robert Edwards, and Alexandre Deur for their hard work and advice. Last but not least, we thank the International Advisory Committee for their very useful inputs to the CD12 program. The organizers thank the excellent logistic and administrative support provided by the Jefferson Lab Conference Staff, Ruth Bizot, Cynthia Lockwood, Stephanie Vermeire, Marti Hightower and MeLaina Evans, and the Conference Secretary Mary Fox, which was instrumental for the success of the organization of CD12. We thank Joanna Griffin for the poster design. CD12 was primarily sponsored by Jefferson Lab, along with generous supports from Old Dominion University and the European Physics Journal. The CD12 homepage is located at http://www.jlab.org/conference/CD12 The upcoming Chiral Dynamics Workshop will take place in Pisa, Italy, in 2015. We thank Laura Marcucci and Michele Viviani for graciously taking the baton from us. Jose Goity and Jianping Chen

  5. 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.

  6. 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...

  7. 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....

  8. Exciton Correlations in Intramolecular Singlet Fission.

    Science.gov (United States)

    Sanders, Samuel N; Kumarasamy, Elango; Pun, Andrew B; Appavoo, Kannatassen; Steigerwald, Michael L; Campos, Luis M; Sfeir, Matthew Y

    2016-06-15

    We have synthesized a series of asymmetric pentacene-tetracene heterodimers with a variable-length conjugated bridge that undergo fast and efficient intramolecular singlet fission (iSF). These compounds have distinct singlet and triplet energies, which allow us to study the spatial dynamics of excitons during the iSF process, including the significant role of exciton correlations in promoting triplet pair generation and recombination. We demonstrate that the primary photoexcitations in conjugated dimers are delocalized singlets that enable fast and efficient iSF. However, in these asymmetric dimers, the singlet becomes more localized on the lower energy unit as the length of the bridge is increased, slowing down iSF relative to analogous symmetric dimers. We resolve the recombination kinetics of the inequivalent triplets produced via iSF, and find that they primarily decay via concerted processes. By identifying different decay channels, including delayed fluorescence via triplet-triplet annihilation, we can separate transient species corresponding to both correlated triplet pairs and uncorrelated triplets. Recombination of the triplet pair proceeds rapidly despite our experimental and theoretical demonstration that individual triplets are highly localized and unable to be transported across the conjugated linker. In this class of compounds, the rate of formation and yield of uncorrelated triplets increases with bridge length. Overall, these constrained, asymmetric systems provide a unique platform to isolate and study transient species essential for singlet fission, which are otherwise difficult to observe in symmetric dimers or condensed phases.

  9. Basal Dynamics and Internal Structure of Ice Sheets

    Science.gov (United States)

    Wolovick, Michael J.

    The internal structure of ice sheets reflects the history of flow and deformation experienced by the ice mass. Flow and deformation are controlled by processes occurring within the ice mass and at its boundaries, including surface accumulation or ablation, ice rheology, basal topography, basal sliding, and basal melting or freezing. The internal structure and basal environment of ice sheets is studied with ice-penetrating radar. Recently, radar observations in Greenland and Antarctica have imaged large englacial structures rising from near the bed that deform the overlying stratigraphy into anticlines, synclines, and overturned folds. The mechanisms that may produce these structures include basal freeze-on, travelling slippery patches at the ice base, and rheological contrasts within the ice column. In this thesis, I explore the setting and mechanisms that produce large basal stratigraphic structures inside ice sheets. First, I use radar data to map subglacial hydrologic networks that deliver meltwater uphill towards freeze-on structures in East Antarctica. Next, I use a thermomechanical flowline model to demonstrate that trains of alternating slippery and sticky patches can form underneath ice sheets and travel downstream over time. The disturbances to the ice flow field produced by these travelling patches produce stratigraphic folds resembling the observations. I then examine the overturned folds produced by a single travelling sticky patch using a kinematic flowline model. This model is used to interpret stratigraphic measurements in terms of the dynamic properties of basal slip. Finally, I use a simple local one-dimensional model to estimate the thickness of basal freeze-on that can be produced based on the supply of available meltwater, the thermal boundary conditions, ice sheet geometry, and the ice flow regime.

  10. Non Covalent Interactions and Internal Dynamics in Adducts of Freons

    Science.gov (United States)

    Caminati, Walther; Gou, Qian; Evangelisti, Luca; Feng, Gang; Spada, Lorenzo; Vallejo-López, Montserrat; Lesarri, Alberto; Cocinero, Emilio J.

    2014-06-01

    The complexation of chlorofluorocarbons (CFCs) with atmospheric water and pollutants of the atmosphere affects their reactivity and it seems to accelerate, for example, the decomposition rate of freons in the atmosphere [1]. For this reason we characterized shapes, stabilities, nature of the non-covalent interactions, structures and internal dynamics of a number of complexes of CFCs with water and of their dimers or oligomers by rotational spectroscopy. It has been found that hydrogenated CFCs form adducts with other molecules through weak hydrogen bonds (WHBs). Their C-H groups can act as proton donors, enhanced by the electron withdrawing of the halogen atoms, interacting with the electron rich regions of the partner molecules [2]. Also in adducts or oligomers of hydrogenated CFCs the monomer units are held together by nets of WHBs [3]. When CFCs are perhalogenated, the positive electrostatic region ("σ-hole") can interact electrostatically with negative sites of another, or of the same molecular entity, giving rise, according to IUPAC, to the so called halogen bond (HaB). However, it has been observed that when the perhalogenated CFCs has a Π electron system, a lone pair•••Π interaction (Bürgi-Dunitz) is favoured [4]. We describe here the HaBs that CF4 and CF3Cl form with a variety of partner molecules such as water, ammonia, dimethyl ether, etc. Important spectroscopic features outline strong dynamics effects taking place in this kind of complex. References [1] V. Vaida, H. G. Kjaergaard, K. J. Feierabend, Int. Rev. Phys. Chem. 22 (2003) 203. [2] See, for example: W. Caminati, S. Melandri, A. Maris, P. Ottaviani, Angew. Chem. Int. Ed. 45 (2006) 2438. [3] G. Feng, L. Evangelisti, I. Cacelli, L. Carbonaro, G. Prampolini, W. Caminati, Chem. Commun. 50 (2014) 171. [4] Q. Gou, G. Feng, L. Evangelisti, W. Caminati, Angew. Chem. Int. Ed. 52 (2013) 52 11888.

  11. Intra-molecular refrigeration in enzymes

    CERN Document Server

    Briegel, Hans J

    2009-01-01

    We present a simple mechanism for intra-molecular refrigeration, where parts of a molecule are actively cooled below the environmental temperature. We discuss the potential role and applications of such a mechanism in biology, in particular in enzymatic reactions.

  12. Analysis of internal drive train dynamics in a wind turbine

    Science.gov (United States)

    Peeters, Joris L. M.; Vandepitte, Dirk; Sas, Paul

    2006-01-01

    Three types of multibody models are presented for the investigation of the internal dynamics of a drive train in a wind turbine. The first approach is limited to the analysis of torsional vibrations only. Then a rigid multibody model is presented with special focus on the representation of the bearings and gears in the drive train. The generic model implementation can be used for parallel as well as planetary gear stages with both helical and spur gears. Examples for different gear stages describe the use of the presented formulations. Furthermore, the influence of the helix angle and the flexibility of the bearings on the results of eigenmode calculations are discussed. The eigenmodes of a planetary stage are classified as rotational, translational or out-of-plane modes. Thirdly, the extension to a flexible multibody model is presented as a method to include directly the drive train components' flexibilities. Finally, a comparison of two different modelling techniques is discussed for a wind turbine's drive train with a helical parallel gear stage and two planetary gear stages. In addition, the response calculation for a torque input at the generator demonstrates which eigenmodes can be excited through this path. Copyright

  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. Intramolecular competition between n-pair and π-pair hydrogen bonding: Microwave spectrum and internal dynamics of the pyridine–acetylene hydrogen-bonded complex

    Energy Technology Data Exchange (ETDEWEB)

    Mackenzie, Rebecca B.; Dewberry, Christopher T.; Leopold, Kenneth R., E-mail: A.C.Legon@bristol.ac.uk, E-mail: david.tew@bristol.ac.uk, E-mail: kleopold@umn.edu [Department of Chemistry, University of Minnesota, 207 Pleasant St., SE, Minneapolis, Minnesota 55455 (United States); Coulston, Emma; Cole, George C. [Department of Chemistry, University of Exeter, Stocker Road, Exeter EX4 4QD (United Kingdom); Legon, Anthony C., E-mail: A.C.Legon@bristol.ac.uk, E-mail: david.tew@bristol.ac.uk, E-mail: kleopold@umn.edu; Tew, David P., E-mail: A.C.Legon@bristol.ac.uk, E-mail: david.tew@bristol.ac.uk, E-mail: kleopold@umn.edu [Department of Chemistry, School of Chemistry, University of Bristol, Cantock’s Close, Bristol BS8 1TS (United Kingdom)

    2015-09-14

    a-type rotational spectra of the hydrogen-bonded complex formed from pyridine and acetylene are reported. Rotational and {sup 14}N hyperfine constants indicate that the complex is planar with an acetylenic hydrogen directed toward the nitrogen. However, unlike the complexes of pyridine with HCl and HBr, the acetylene moiety in HCCH—NC{sub 5}H{sub 5} does not lie along the symmetry axis of the nitrogen lone pair, but rather, forms an average angle of 46° with the C{sub 2} axis of the pyridine. The a-type spectra of HCCH—NC{sub 5}H{sub 5} and DCCD—NC{sub 5}H{sub 5} are doubled, suggesting the existence of a low lying pair of tunneling states. This doubling persists in the spectra of HCCD—NC{sub 5}H{sub 5}, DCCH—NC{sub 5}H{sub 5}, indicating that the underlying motion does not involve interchange of the two hydrogens of the acetylene. Single {sup 13}C substitution in either the ortho- or meta-position of the pyridine eliminates the doubling and gives rise to separate sets of spectra that are well predicted by a bent geometry with the {sup 13}C on either the same side (“inner”) or the opposite side (“outer”) as the acetylene. High level ab initio calculations are presented which indicate a binding energy of 1.2 kcal/mol and a potential energy barrier of 44 cm{sup −1} in the C{sub 2v} configuration. Taken together, these results reveal a complex with a bent hydrogen bond and large amplitude rocking of the acetylene moiety. It is likely that the bent equilibrium structure arises from a competition between a weak hydrogen bond to the nitrogen (an n-pair hydrogen bond) and a secondary interaction between the ortho-hydrogens of the pyridine and the π electron density of the acetylene.

  15. Accounting for intra-molecular vibrational modes in open quantum system description of molecular systems.

    Science.gov (United States)

    Roden, Jan; Strunz, Walter T; Whaley, K Birgitta; Eisfeld, Alexander

    2012-11-28

    Electronic-vibrational dynamics in molecular systems that interact with an environment involve a large number of degrees of freedom and are therefore often described by means of open quantum system approaches. A popular approach is to include only the electronic degrees of freedom into the system part and to couple these to a non-Markovian bath of harmonic vibrational modes that is characterized by a spectral density. Since this bath represents both intra-molecular and external vibrations, it is important to understand how to construct a spectral density that accounts for intra-molecular vibrational modes that couple further to other modes. Here, we address this problem by explicitly incorporating an intra-molecular vibrational mode together with the electronic degrees of freedom into the system part and using the Fano theory for a resonance coupled to a continuum to derive an "effective" bath spectral density, which describes the contribution of intra-molecular modes. We compare this effective model for the intra-molecular mode with the method of pseudomodes, a widely used approach in simulation of non-Markovian dynamics. We clarify the difference between these two approaches and demonstrate that the respective resulting dynamics and optical spectra can be very different.

  16. Recording Intramolecular Mechanics during the Manipulation of a Large Molecule

    Science.gov (United States)

    Moresco, Francesca; Meyer, Gerhard; Rieder, Karl-Heinz; Tang, Hao; Gourdon, André; Joachim, Christian

    2001-08-01

    The technique of single atom manipulation by means of the scanning tunneling microscope (STM) applies to the controlled displacement of large molecules. By a combined experimental and theoretical work, we show that in a constant height mode of manipulation the STM current intensity carries detailed information on the internal mechanics of the molecule when guided by the STM tip. Controlling and time following the intramolecular behavior of a large molecule on a surface is the first step towards the design of molecular tunnel-wired nanorobots.

  17. Recording Intramolecular Mechanics during the Manipulation of a Large Molecule

    Energy Technology Data Exchange (ETDEWEB)

    Moresco, Francesca; Meyer, Gerhard; Rieder, Karl-Heinz; Tang, Hao; Gourdon, Andre; Joachim, Christian

    2001-08-20

    The technique of single atom manipulation by means of the scanning tunneling microscope (STM) applies to the controlled displacement of large molecules. By a combined experimental and theoretical work, we show that in a constant height mode of manipulation the STM current intensity carries detailed information on the internal mechanics of the molecule when guided by the STM tip. Controlling and time following the intramolecular behavior of a large molecule on a surface is the first step towards the design of molecular tunnel-wired nanorobots.

  18. Recording intramolecular mechanics during the manipulation of a large molecule.

    Science.gov (United States)

    Moresco, F; Meyer, G; Rieder, K H; Tang, H; Gourdon, A; Joachim, C

    2001-08-20

    The technique of single atom manipulation by means of the scanning tunneling microscope (STM) applies to the controlled displacement of large molecules. By a combined experimental and theoretical work, we show that in a constant height mode of manipulation the STM current intensity carries detailed information on the internal mechanics of the molecule when guided by the STM tip. Controlling and time following the intramolecular behavior of a large molecule on a surface is the first step towards the design of molecular tunnel-wired nanorobots.

  19. Dynamics and control designs for internal thermally coupled distillation columns with different purities, Part 1: Open loop dynamic behaviors

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    The open loop dynamic behaviors of internal thermally coupled distillation column with four different purities (low-,moderate-, high- and very high-purity) are studied. These dynamic behaviors are characterized by strong asymmetric non-linearity, high sensitivity to operation conditions change and distinct inverse response. With the increase of purity, these dynamic behaviors are intensified and become more complex, which easily lead to the mismatch between linear model and plant and also change the relationship between manipulated and controlled variables.

  20. Molecular internal dynamics studied by quantum path interferences in high order harmonic generation

    Energy Technology Data Exchange (ETDEWEB)

    Zaïr, Amelle, E-mail: azair@imperial.ac.uk [Imperial College London, Department of Physics, Blackett Laboratory Laser Consortium, London SW7 2AZ (United Kingdom); Siegel, Thomas; Sukiasyan, Suren; Risoud, Francois; Brugnera, Leonardo; Hutchison, Christopher [Imperial College London, Department of Physics, Blackett Laboratory Laser Consortium, London SW7 2AZ (United Kingdom); Diveki, Zsolt; Auguste, Thierry [Service des Photons, Atomes et Molécules, CEA-Saclay, 91191 Gif-sur-Yvette (France); Tisch, John W.G. [Imperial College London, Department of Physics, Blackett Laboratory Laser Consortium, London SW7 2AZ (United Kingdom); Salières, Pascal [Service des Photons, Atomes et Molécules, CEA-Saclay, 91191 Gif-sur-Yvette (France); Ivanov, Misha Y.; Marangos, Jonathan P. [Imperial College London, Department of Physics, Blackett Laboratory Laser Consortium, London SW7 2AZ (United Kingdom)

    2013-03-12

    Highlights: ► Electronic trajectories in high order harmonic generation encodes attosecond and femtosecond molecular dynamical information. ► The observation of these quantum paths allows us to follow nuclear motion after ionization. ► Quantum paths interference encodes a signature of superposition of ionization channels. ► Quantum paths interference encodes a signature of transfer of population between channels due to laser coupling. ► Quantum paths interference is a promising technique to resolve ultra-fast dynamical processes after ionization. - Abstract: We investigate how short and long electron trajectory contributions to high harmonic emission and their interferences give access to information about intra-molecular dynamics. In the case of unaligned molecules, we show experimental evidence that the long trajectory contribution is more dependent upon the molecular species than the short one, providing a high sensitivity to cation nuclear dynamics from 100’s of as to a few fs after ionisation. Using theoretical approaches based on the strong field approximation and numerical integration of the time dependent Schrödinger equation, we examine how quantum path interferences encode electronic motion when the molecules are aligned. We show that the interferences are dependent upon which ionisation channels are involved and any superposition between them. In particular, quantum path interferences can encode signatures of electron dynamics if the laser field drives a coupling between the channels. Hence, molecular quantum path interferences are a promising method for attosecond spectroscopy, allowing the resolution of ultra-fast charge migration in molecules after ionisation in a self-referenced manner.

  1. Studying the Dynamics of TCR Internalization at the Immune Synapse.

    Science.gov (United States)

    Calleja, Enrique; Alarcón, Balbino; Oeste, Clara L

    2017-01-01

    Establishing a stable interaction between a T cell and an antigen presenting cell (APC) involves the formation of an immune synapse (IS). It is through this structure that the T cell can integrate all the signals provided by the APC. The IS also serves as a mechanism for TCR downregulation through internalization. Here, we describe methods for visualizing MHC-engaged T cell receptor (TCR) internalization from the IS in human cell lines and mouse primary T cells by confocal fluorescence microscopy techniques.

  2. Intramolecular Cycloaddition of Imines of Cysteine Derivatives

    Directory of Open Access Journals (Sweden)

    Teresa M. V. D. Pinho e Melo

    1998-02-01

    Full Text Available Azomethine ylides were generated from Schiffs bases of S-allylcysteine methyl ester and their intramolecular 1,3-dipolar cycloadditions were studied. These reactions led to the synthesis of thieno[3,4-b]pyrrole derivatives in good yield.

  3. Palladium-Catalyzed Intramolecular Aminofluorination of Styrenes%Palladium-Catalyzed Intramolecular Aminofluorination of Styrenes

    Institute of Scientific and Technical Information of China (English)

    徐涛; 邱水发; 刘国生

    2011-01-01

    A novel palladium-catalyzed intramolecular oxidative aminofluorination of styrenes has been developed by using NFSI as fluorinating reagent. This reaction represented an efficient method for the synthesis of 2-aryl-3-fluoropyrrolidine derivatives.

  4. Decomposition of molecular motions into translational, rotational, and intramolecular parts by a projection operator technique

    DEFF Research Database (Denmark)

    Hansen, Flemming Yssing; Taub, H.

    2009-01-01

    The motion of the atoms in a molecule may be described as a superposition of translational motion of the molecular center-of-mass, rotational motion about the principal molecular axes, and an intramolecular motion that may be associated with vibrations and librations as well as molecular conforma......The motion of the atoms in a molecule may be described as a superposition of translational motion of the molecular center-of-mass, rotational motion about the principal molecular axes, and an intramolecular motion that may be associated with vibrations and librations as well as molecular...... conformational changes. We have constructed projection operators that use the atomic coordinates and velocities at any two times, t=0 and a later time t, to determine the molecular center-of-mass, rotational, and intramolecular motions in a molecular dynamics simulation. This model-independent technique...

  5. 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...

  6. 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...

  7. International conference on dynamical systems and game theory

    CERN Document Server

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

    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

  8. 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).

  9. 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.

  10. International Conference on Numerical Grid Generation in Computational Fluid Dynamics

    Science.gov (United States)

    1989-04-30

    Grun Convex Computer Corporation Brunnenstr. 17 701 Piano Road 8049 Bachenhausen Richardson Germany TX 75081 Chunyuan Gu J. E.Holcomb Dept. of Gas...Lab System Dynamics Inc. L-95, PO Box 808 1211 N.W. 10th Avenue Livermore, CA 94550 Gainesville FL 32601 Bernadette Palmero Azine Renzo Universite de

  11. Effect of internal viscosity on Brownian dynamics of DNA molecules in shear flow.

    Science.gov (United States)

    Yang, Xiao-Dong; Melnik, Roderick V N

    2007-04-01

    The results of Brownian dynamics simulations of a single DNA molecule in shear flow are presented taking into account the effect of internal viscosity. The dissipative mechanism of internal viscosity is proved necessary in the research of DNA dynamics. A stochastic model is derived on the basis of the balance equation for forces acting on the chain. The Euler method is applied to the solution of the model. The extensions of DNA molecules for different Weissenberg numbers are analyzed. Comparison with the experimental results available in the literature is carried out to estimate the contribution of the effect of internal viscosity.

  12. UNESCO and World Heritage: National Contexts, International Dynamics

    DEFF Research Database (Denmark)

    Andersen, Casper; Kozymka, Irena

    contexts that shape the ideas and practices of the World Heritage system. This includes examining the influence of the World Heritage system on the behaviour of nation states, both domestically and internationally, but also shedding light on how national traditions of heritage management and national...... particularly patchy. This includes studies of East and North Africa, Asia and the Pacific, Europe and North America, and the former Soviet Union....

  13. Ultrafast solvation dynamics at internal site of staphylococcal nuclease investigated by site-directed mutagenesis

    CERN Document Server

    Guang-yu, Gao; Wei, Wang; Shu-feng, Wang; Zhong, Dongping; Qi-huang, Gong

    2014-01-01

    Solvation is essential for protein activities. To study internal solvation of protein, site-directed mutagenesis is applied. Intrinsic fluorescent probe, tryptophan, is inserted into desired position inside protein molecule for ultrafast spectroscopic study. Here we review this unique method for protein dynamics researches. We introduce the frontiers of protein solvation, site-directed mutagenesis, protein stability and characteristics, and the spectroscopic methods. Then we present time-resolved spectroscopic dynamics of solvation dynamics inside caves of active sites. The studies are carried out on a globular protein, staphylococcal nuclease. The solvation at internal sites of the caves indicate clear characteristics of local environment. These solvation behaviors correlated to the enzyme activity directly.

  14. 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...

  15. Dynamical analysis of mesoscale eddy-induced ocean internal waves using linear theories

    Institute of Scientific and Technical Information of China (English)

    XU Qing; ZHENG Quanan; LIN Hui; LIU Yuguang; SONG YTony; YUAN Yeli

    2008-01-01

    This study aims to explore generation mechanisms of the ocean internal wave using the dynamical analysis methods based on linear theories. Historical cruise measurements and recent synthetic aperture radar (SAR) observations of mesoscale eddies with diame-ter of several tens of kilometers to hundreds of kilometers show that the internal wave packets with wavelength of hundreds of me-ters to kilometer exist inside the mesoscale eddies. This coexistence phenomenon and inherent links between the two different scale processes are revealed in the solutions of governing equations and boundary conditions for the internal wave disturbance with a horizontally slowly variable amplitude in a cylindrical coordinate system. The theoretical solutions indicate that the instability of eddy current field provides the dynamical mechanism to internal wave generation. The derived dispersion relation indicates that the internal wave propagation is modified by the eddy current field structure. The energy equation of the internal waves clearly shows the internal wave energy increment comes from the eddy. The theoretical models are used to explain the observation of the mesoscale ed-dy-induced internal waves off the Norwegian coast. The two-dimensional waveform solution of the anticyclonic eddy-induced internal wave packet appears as ring-shaped curves, which contains the typical features of eddy stream lines. The comparison of theoretical solutions to the structure of the internal wave packets on SAR image shows a good agreement on the major features.

  16. Intramolecular Association within the SAFT Framework

    DEFF Research Database (Denmark)

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

    2011-01-01

    sites. We show that the resulting equations from the two approaches are equivalent, and use their work as a basis for developing a new general theory. The approach used by Ghonasgi and Chapman is based on mass balances and an infinite dilution result and provides the equations needed to determine...... 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...... association, and using this approach we obtain an expression for the Helmholtz free energy that is valid also at non-equilibrium states (with respect to hydrogen bonds), which is very useful when calculating derivatives....

  17. 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...

  18. An unusual intramolecular trans-amidation.

    Science.gov (United States)

    Rivera, Heriberto; Dhar, Sachin; La Clair, James J; Tsai, Shiou-Chuan; Burkart, Michael D

    2016-06-23

    Polyketide biosynthesis engages a series of well-timed biosynthetic operations to generate elaborate natural products from simple building blocks. Mimicry of these processes has offered practical means for total synthesis and provided a foundation for reaction discovery. We now report an unusual intramolecular trans-amidation reaction discovered while preparing stabilized probes for the study of actinorhodin biosynthesis. This rapid cyclization event offers insight into the natural cyclization process inherent to the biosynthesis of type II polyketide antibiotics.

  19. Internal Dynamics of a Twin-layer Solar Prominence

    Science.gov (United States)

    Xia, C.; Keppens, R.

    2016-07-01

    Modern observations revealed rich dynamics within solar prominences. The globally stable quiescent prominences, characterized by the presence of thin vertical threads and falling knobs, are frequently invaded by small rising dark plumes. These dynamic phenomena are related to magnetic Rayleigh-Taylor instability, since prominence matter, 100 times denser than surrounding coronal plasma, is lifted against gravity by weak magnetic field. To get a deeper understanding of the physics behind these phenomena, we use three-dimensional magnetohydrodynamic simulations to investigate the nonlinear magnetoconvective motions in a twin-layer prominence in a macroscopic model from chromospheric layers up to 30 Mm height. The properties of simulated falling “fingers” and uprising bubbles are consistent with those in observed vertical threads and rising plumes in quiescent prominences. Both sheets of the twin-layer prominence show a strongly coherent evolution due to their magnetic connectivity, and demonstrate collective kink deformation. Our model suggests that the vertical threads of the prominence as seen in an edge-on view, and the apparent horizontal threads of the filament when seen top-down are different appearances of the same structures. Synthetic images of the modeled twin-layer prominence reflect the strong degree of mixing established over the entire prominence structure, in agreement with the observations.

  20. Quantification of intramolecular nonbonding interactions in organochalcogens.

    Science.gov (United States)

    Roy, Dipankar; Sunoj, Raghavan B

    2006-05-04

    Intramolecular nonbonding interactions between chalcogen atoms in a series of ortho substituted arylselenides (S/O...Se-Y, with Y = -Me, -CN, -Cl, and -F) are quantified using the coupled cluster CCSD(T)/cc-pVDZ level of theory. A homodesmic reaction method as well as an ortho-para approach are employed in evaluating the strength of intramolecular interactions. Comparison of the results obtained using the ab initio MP2 method and pure and hybrid density functional theories are performed with that of the coupled cluster values to assess the quality of different density functionals in evaluating the strength of nonbonding interactions. The interaction energies are found to be higher when the thioformyl group acts as the donor and the Se-F bond acts as the acceptor. In a given series with the same donor atom, the strength of the interaction follows the order Me < CN < Cl < F, exhibiting fairly high sensitivity to the group attached to selenium (Se-Y). Analysis of electron density at the S/O...Se bond critical point within the Atoms in Molecule framework shows a very good correlation with the computed intramolecular interaction energies.

  1. Intramolecular hydrogen bonding in medicinal chemistry.

    Science.gov (United States)

    Kuhn, Bernd; Mohr, Peter; Stahl, Martin

    2010-03-25

    The formation of intramolecular hydrogen bonds has a very pronounced effect on molecular structure and properties. We study both aspects in detail with the aim of enabling a more rational use of this class of interactions in medicinal chemistry. On the basis of exhaustive searches in crystal structure databases, we derive propensities for intramolecular hydrogen bond formation of five- to eight-membered ring systems of relevance in drug discovery. A number of motifs, several of which are clearly underutilized in drug discovery, are analyzed in more detail by comparing small molecule and protein-ligand X-ray structures. To investigate effects on physicochemical properties, sets of closely related structures with and without the ability to form intramolecular hydrogen bonds were designed, synthesized, and characterized with respect to membrane permeability, water solubility, and lipophilicity. We find that changes in these properties depend on a subtle balance between the strength of the hydrogen bond interaction, geometry of the newly formed ring system, and the relative energies of the open and closed conformations in polar and unpolar environments. A number of general guidelines for medicinal chemists emerge from this study.

  2. Evolution of the global internal dynamics of a living cell nucleus during interphase.

    Science.gov (United States)

    Suissa, M; Place, C; Goillot, E; Freyssingeas, E

    2009-07-22

    Progress in cellular biology based on fluorescent microscopy techniques, shows that the spatial organization of the nucleus is dynamic. This dynamic is very complex and involves a multitude of phenomena that occur on very different time and size scales. Using an original light scattering experimental device, we investigated the global internal dynamics of the nucleus of a living cell according to the phases of the cell cycle. This dynamic presents two different and independent kinds of relaxation that are well separated in time and specific to the phase of the cell cycle.

  3. The Dynamics of Flat Surface Internal Geophysical Waves with Currents

    Science.gov (United States)

    Compelli, Alan; Ivanov, Rossen I.

    2016-08-01

    A two-dimensional water wave system is examined consisting of two discrete incompressible fluid domains separated by a free common interface. In a geophysical context this is a model of an internal wave, formed at a pycnocline or thermocline in the ocean. The system is considered as being bounded at the bottom and top by a flatbed and wave-free surface respectively. A current profile with depth-dependent currents in each domain is considered. The Hamiltonian of the system is determined and expressed in terms of canonical wave-related variables. Limiting behaviour is examined and compared to that of other known models. The linearised equations as well as long-wave approximations are presented.

  4. 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.

  5. The Dynamics of Flat Surface Internal Geophysical Waves with Currents

    CERN Document Server

    Compelli, Alan

    2016-01-01

    A two-dimensional water wave system is examined consisting of two discrete incompressible fluid domains separated by a free common interface. In a geophysical context this is a model of an internal wave, formed at a pycnocline or thermocline in the ocean. The system is considered as being bounded at the bottom and top by a flatbed and wave-free surface respectively. A current profile with depth-dependent currents in each domain is considered. The Hamiltonian of the system is determined and expressed in terms of canonical wave-related variables. Limiting behaviour is examined and compared to that of other known models. The linearised equations as well as long-wave approximations are presented.

  6. Intramolecular hydrophobic interactions are critical mediators of STAT5 dimerization

    Science.gov (United States)

    Fahrenkamp, Dirk; Li, Jinyu; Ernst, Sabrina; Schmitz-van de Leur, Hildegard; Chatain, Nicolas; Küster, Andrea; Koschmieder, Steffen; Lüscher, Bernhard; Rossetti, Giulia; Müller-Newen, Gerhard

    2016-10-01

    STAT5 is an essential transcription factor in hematopoiesis, which is activated through tyrosine phosphorylation in response to cytokine stimulation. Constitutive activation of STAT5 is a hallmark of myeloid and lymphoblastic leukemia. Using homology modeling and molecular dynamics simulations, a model of the STAT5 phosphotyrosine-SH2 domain interface was generated providing first structural information on the activated STAT5 dimer including a sequence, for which no structural information is available for any of the STAT proteins. We identified a novel intramolecular interaction mediated through F706, adjacent to the phosphotyrosine motif, and a unique hydrophobic interface on the surface of the SH2 domain. Analysis of corresponding STAT5 mutants revealed that this interaction is dispensable for Epo receptor-mediated phosphorylation of STAT5 but essential for dimer formation and subsequent nuclear accumulation. Moreover, the herein presented model clarifies molecular mechanisms of recently discovered leukemic STAT5 mutants and will help to guide future drug development.

  7. 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

  8. 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...

  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

    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.

  10. 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.

  11. Taking Einstein seriously: Relativistic coupling of internal and center of mass dynamics

    CERN Document Server

    Krause, Dennis E

    2016-01-01

    Einstein's famous equation $E_{\\rm rest}=mc^2$ for the rest energy of a system with mass $m$ requires that the internal energy of the system be included in $m$. Pursuing this idea using Lagrangian and Hamiltonian dynamics yields a relativistic coupling between the center of mass motion and the internal dynamics of the system. Here we explore the consequences of this coupling, first classically, where we find that the dynamics of the system is time dilated when moving relative to another inertial frame. We then apply the dynamics to a quantum 2-level atom bound in a 1-dimensional infinite potential well, and show that the coupling produces collapses and revivals in quantum interference.

  12. Fundamental problems of modeling the dynamics of internal gravity waves with applications to the Arctic Basin

    CERN Document Server

    Bulatov, Vitaly V

    2012-01-01

    In this paper, we consider fundamental problems of the dynamics of internal gravity waves. We present analytical and numerical algorithms for calculating the wave fields for a set of values of the parameters, as observed in the ocean. We show that our mathematical models can describe the wave dynamics of the Arctic Basin, taking into account the actual physical characteristics of sea water, topography of its floor, etc. The numerical and analytical results show that the internal gravity waves have a significant effect on underwater sea objects in the Arctic Basin.

  13. Dynamical systems with internal degrees of freedom in non-Euclidean spaces

    OpenAIRE

    Sławianowski, J. J.; Kovalchuk, V.; Gołubowska, B.; Martens, A; Rożko, E. E.

    2008-01-01

    Presented is description of kinematics and dynamics of material points with internal degrees of freedom moving in a Riemannian manifold. The models of internal degrees of freedom we concentrate on are based on the orthogonal and affine groups. Roughly speaking, we consider infinitesimal gyroscopes and homogeneously deformable gyroscopes (affienly-rigid bodies) in curved manifolds. We follow our earlier models of extended rigid and affinely-rigid bodies moving in a flat space. It is well known...

  14. 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.

  15. 1:2 INTERNAL RESONANCE OF COUPLED DYNAMIC SYSTEM WITH QUADRATIC AND CUBIC NONLINEARITIES

    Institute of Scientific and Technical Information of China (English)

    陈予恕; 杨彩霞; 吴志强; 陈芳启

    2001-01-01

    The 1:2 internal resonance of coupled dynamic system with quadratic and cubic nonlinearities is studied. The normal forms of this system in 1: 2 internal resonance were derived by using the direct method of normal form. In the normal forms, quadratic and cubic nonlinearities were remained. Based on a new convenient transformation technique, the 4-dimension bifurcation equations were reduced to 3-dimension. A bifurcation equation with one-dimension was obtained. Then the bifurcation behaviors of a universal unfolding were studied by using the singularity theory. The method of this paper can be applied to analyze the bifurcation behavior in strong internal resonance on 4-dimension center manifolds.

  16. Intramolecular energy transfer reactions in polymetallic

    Energy Technology Data Exchange (ETDEWEB)

    Petersen, J.

    1990-11-01

    This report is concerned with intramolecular, energy-transfer reactions. The concept of preparing synthetically a complex molecular species, capable of absorbing a photon at one metal center (antenna fragment), transferring that energy to a second metal center (reactive fragment) via a bridging ligand was first reported by our group in 1979. It is now apparent that a major emphasis in inorganic chemistry in the future will involve these types of molecular ensembles. Complexes discussed include Rh, Ru, and Cu complexes. 23 refs., 14 tabs.

  17. 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 increase...

  18. Symplectic integration of closed chain rigid body dynamics with internal coordinate equations of motion

    Science.gov (United States)

    Mazur, Alexey K.

    1999-07-01

    Internal coordinate molecular dynamics (ICMD) is a recent efficient method for modeling polymer molecules which treats them as chains of rigid bodies rather than ensembles of point particles as in Cartesian MD. Unfortunately, it is readily applicable only to linear or tree topologies without closed flexible loops. Important examples violating this condition are sugar rings of nucleic acids, proline residues in proteins, and also disulfide bridges. This paper presents the first complete numerical solution of the chain closure problem within the context of ICMD. The method combines natural implicit fixation of bond lengths and bond angles by the choice of internal coordinates with explicit constraints similar to Cartesian dynamics used to maintain the chain closure. It is affordable for large molecules and makes possible 3-5 times faster dynamics simulations of molecular systems with flexible rings, including important biological objects like nucleic acids and disulfide-bonded proteins.

  19. 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.

  20. A stochastic model for the indicated pressure process and the dynamics of the internal combustion engine

    Energy Technology Data Exchange (ETDEWEB)

    Rizzoni, G. (Michigan Univ., Ann Arbor, MI (USA). Dept. of Electrical Engineering and Computer Science)

    1989-08-01

    In-cylinder gas pressure has long been recognized as a fundamental measure of performance in the internal combustion engine. Among the issues that have been the subject of research in recent years is the study of the effects cyclic combustion variability has on the cycle-to-cycle and cylinder-to-cylinder fluctuations in combustion pressures. Some of the research problems pertaining to cyclic combustion variability are to reformulate from a perspective markedly different from the fluid dynamic and thermodynamic models which traditionally characterize this research: a system viewpoint is embraced to construct a stochastic model for the indicated pressure process and the dynamics of the internal combustion engine. First a deterministic model for the dynamics of the engine is described; then a stochastic model is proposed for the cylinder pressure process. The deterministic model and the stochastic representation are then tied together in a Kalman filter model. Experimental results are discussed to validate the models.

  1. Mental imagery of speech and movement implicates the dynamics of internal forward models

    Directory of Open Access Journals (Sweden)

    Xing eTian

    2010-10-01

    Full Text Available The classical concept of efference copies in the context of internal forward models has stimulated productive research in cognitive science and neuroscience. There are compelling reasons to argue for such a mechanism, but finding direct evidence in the human brain remains difficult. Here we investigate the dynamics of internal forward models from an unconventional angle: mental imagery, assessed while recording high temporal resolution neuronal activity using magnetoencephalography (MEG. We compare two overt and covert tasks; our covert, mental imagery tasks are unconfounded by overt input/output demands – but in turn necessitate the development of appropriate multi-dimensional topographic analyses. Finger tapping (studies 1-2 and speech experiments (studies 3-5 provide temporally constrained results that implicate the estimation of an efference copy. We suggest that one internal forward model over parietal cortex subserves the kinesthetic feeling in motor imagery. Secondly, observed auditory neural activity ~170 ms after motor estimation in speech experiments (studies 3-5 demonstrates the anticipated auditory consequences of planned motor commands in a second internal forward model in imagery of speech production. Our results provide neurophysiological evidence from the human brain in favor of internal forward models deploying efference copies in somatosensory and auditory cortex, in finger tapping and speech production tasks, respectively, and also suggest the dynamics and sequential updating structure of internal forward models.

  2. Dynamic analysis of internal and external mental sweating by optical coherence tomography.

    Science.gov (United States)

    Ohmi, Masato; Tanigawa, Motomu; Yamada, Akihiro; Ueda, Yoshihiro; Haruna, Masamitsu

    2009-01-01

    Mental sweating is human sweating that is accelerated via the sympathetic nerve by application of mental or physical stress. In the neurosciences, there is keen interest in this type of sweating, because the amount of sweat in response to a stress applied to a volunteer directly reflects activity of the sympathetic nerve. It is therefore of particular value that optical coherence tomography (OCT) can provide clear in vivo imaging of the spiral lumen of an eccrin sweat gland in the epidermis with a spatial resolution around 10 mum. We demonstrate dynamic OCT of mental sweating of an eccrin sweat gland on a human fingertip, where the sweating dynamics can be tracked by time-sequential OCT images with a frame spacing of one second. An instantaneous amount of sweat stored in the spiral lumen is evaluated quantitatively in each OCT image, resulting in time variation measurements of excess sweat in response to mental or physical stress. In the dynamic OCT of mental sweating, as demonstrated here, we note for the first time internal sweating without ejection of excess sweat from the spiral lumen to the skin surface. Internal sweating has not been previously detected without the availability of our dynamic OCT technique. Until now, it has been commonly accepted that sweating is always accompanied with ejection of excess sweat to the skin surface. On the basis of our findings reported here, this type of sweating should now be referred to as external sweating. In this study, we demonstrate that internal sweating occurs more often in the case where mental stress is applied to a volunteer, and that it is more useful for evaluation of activity of the sympathetic nerve. The dynamic OCT for both external and internal sweating is demonstrated.

  3. Effect of Upward Internal Flow on Dynamics of Riser Model Subject to Shear Current

    Institute of Scientific and Technical Information of China (English)

    CHEN Zheng-shou; KIM Wu-joan; XIONG Cong-bo

    2012-01-01

    Numerical study about vortex-induced vibration (VIV) related to a flexible riser model in consideration of internal flow progressing inside has been performed.The main objective of this work is to investigate the coupled fluid-structure interaction (FSI) taking place between tensioned riser model,external shear current and upward-progressing internal flow (from ocean bottom to surface).A CAE technology behind the current research which combines structural softwàre with the CFD technology has been proposed.According to the result from dynamic analysis,it has been found that the existence of upward-progressing internal flow does play an important role in determining the vibration mode (/dominant frequency),vibration intensity and the magnitude of instantaneous vibration amplitude,when the velocity ratio of internal flow against external current is relatively high.As a rule,the larger the velocity of internal flow is,the more it contributes to the dynamic vibration response of the flexible riser model.In addition,multi-modal vibration phenomenon has been widely observed,for asymmetric curvature along the riser span emerges in the case of external shear current being imposed.

  4. The intramolecular click reaction using 'carbocontiguous' precursors.

    Science.gov (United States)

    Patil, Pravin C; Luzzio, Frederick A

    2017-07-20

    The synthesis and utilization of all carbon-chain 'carbocontiguous' azidoalkynyl precursors for an intramolecular click reaction is described. The substrates contain both azidoalkyl and ethynylmethyl groups which are conjoined by a 2-(phenylsulfonylmethyl)-4,5-diphenyloxazole lynchpin and are suitably disposed for ring closure. On promotion by copper salts, a number of cyclic click products having the 1,4-disubstituted endo-fused triazole component and the 4,5-diphenyloxazole component are obtained. In one case, removal of the phenylsulfonylmethyl group from the substrate prior to cyclization gave the 1,5-disubstituted exo-fused triazole. The utilization of CuSO4/sodium ascorbate system appears to be the optimal conditions for closure/cyclization and afforded the cyclized products in yields of 84-95%.

  5. Dynamic regulatory on/off minimization for biological systems under internal temporal perturbations

    Directory of Open Access Journals (Sweden)

    Kleessen Sabrina

    2012-03-01

    Full Text Available Abstract Background Flux balance analysis (FBA together with its extension, dynamic FBA, have proven instrumental for analyzing the robustness and dynamics of metabolic networks by employing only the stoichiometry of the included reactions coupled with adequately chosen objective function. In addition, under the assumption of minimization of metabolic adjustment, dynamic FBA has recently been employed to analyze the transition between metabolic states. Results Here, we propose a suite of novel methods for analyzing the dynamics of (internally perturbed metabolic networks and for quantifying their robustness with limited knowledge of kinetic parameters. Following the biochemically meaningful premise that metabolite concentrations exhibit smooth temporal changes, the proposed methods rely on minimizing the significant fluctuations of metabolic profiles to predict the time-resolved metabolic state, characterized by both fluxes and concentrations. By conducting a comparative analysis with a kinetic model of the Calvin-Benson cycle and a model of plant carbohydrate metabolism, we demonstrate that the principle of regulatory on/off minimization coupled with dynamic FBA can accurately predict the changes in metabolic states. Conclusions Our methods outperform the existing dynamic FBA-based modeling alternatives, and could help in revealing the mechanisms for maintaining robustness of dynamic processes in metabolic networks over time.

  6. Preface to Special Topic: Invited Papers of the 3rd International Conference on Ultrafast Structural Dynamics.

    Science.gov (United States)

    Johnson, S L

    2016-03-01

    The ability to visualize the real-time dynamics of atomic, magnetic, and electronic structure is widely recognized in many fields as a key element underpinning many important processes in chemistry, materials science, and biology. The need for an improved understanding of such processes becomes acute as energy conversion processes on fast time scales become increasingly relevant to problems in science and technology. This special issue, containing invited papers from participants at the 3rd International Conference on Ultrafast Structural Dynamics held June 10-12, 2015 in Zurich, Switzerland, discusses several recent developments in this area.

  7. Hybrid internal model control and proportional control of chaotic dynamical systems

    Institute of Scientific and Technical Information of China (English)

    齐冬莲; 姚良宾

    2004-01-01

    A new chaos control method is proposed to take advantage of chaos or avoid it. The hybrid Internal Model Control and Proportional Control learning scheme are introduced. In order to gain the desired robust performance and ensure the system's stability, Adaptive Momentum Algorithms are also developed. Through properly designing the neural network plant model and neural network controller, the chaotic dynamical systems are controlled while the parameters of the BP neural network are modified. Taking the Lorenz chaotic system as example, the results show that chaotic dynamical systems can be stabilized at the desired orbits by this control strategy.

  8. Preface to Special Topic: Invited Papers of the 3rd International Conference on Ultrafast Structural Dynamics

    Directory of Open Access Journals (Sweden)

    S. L. Johnson

    2016-03-01

    Full Text Available The ability to visualize the real-time dynamics of atomic, magnetic, and electronic structure is widely recognized in many fields as a key element underpinning many important processes in chemistry, materials science, and biology. The need for an improved understanding of such processes becomes acute as energy conversion processes on fast time scales become increasingly relevant to problems in science and technology. This special issue, containing invited papers from participants at the 3rd International Conference on Ultrafast Structural Dynamics held June 10–12, 2015 in Zurich, Switzerland, discusses several recent developments in this area.

  9. Hybrid internal model control and proportional control of chaotic dynamical systems.

    Science.gov (United States)

    Qi, Dong-lian; Yao, Liang-bin

    2004-01-01

    A new chaos control method is proposed to take advantage of chaos or avoid it. The hybrid Internal Model Control and Proportional Control learning scheme are introduced. In order to gain the desired robust performance and ensure the system's stability, Adaptive Momentum Algorithms are also developed. Through properly designing the neural network plant model and neural network controller, the chaotic dynamical systems are controlled while the parameters of the BP neural network are modified. Taking the Lorenz chaotic system as example, the results show that chaotic dynamical systems can be stabilized at the desired orbits by this control strategy.

  10. Both Inter- and Intramolecular Coupling of O-H Groups Determine the Vibrational Response of the Water/Air Interface

    CERN Document Server

    Schaefer, Jan; Nagata, Yuki; Bonn, Mischa

    2016-01-01

    Vibrational coupling is relevant not only for dissipation of excess energy after chemical reactions but also for elucidating molecular structure and dynamics. It is particularly important for OH stretch vibrational spectra of water, for which it is known that in bulk both intra- and intermolecular coupling alter the intensity and line shape of the spectra. In contrast with bulk, the unified picture of the inter/intra-molecular coupling of OH groups at the water-air interface has been lacking. Here, combining sum-frequency generation experiments and simulation for isotopically diluted water and alcohols, we unveil effects of inter- and intramolecular coupling on the vibrational spectra of interfacial water. Our results show that both inter- and intramolecular coupling contribute to the OH stretch vibrational response of the neat H2O surface, with intramolecular coupling generating a double-peak feature, while the intermolecular coupling induces a significant red shift in the OH stretch response.

  11. First-Principle Molecular Dynamics Study of Selected Schiff and Mannich Bases:  Application of Two-Dimensional Potential of Mean Force to Systems with Strong Intramolecular Hydrogen Bonds.

    Science.gov (United States)

    Jezierska, Aneta; Panek, Jarosław J

    2008-03-01

    Car-Parrinello Molecular Dynamics simulations were performed for selected anharmonic systems, i.e., Schiff and Mannich base-type compounds, to investigate the vibrational properties associated with O-H stretching. All calculations were performed in the gas phase to compare them with available experimental data. First the vibrational properties of the two compounds were analyzed on the basis of well-established approaches:  Fourier transformation of the autocorrelation function of both the atomic velocities and dipole moments. Then path integral molecular dynamics simulations were performed to demonstrate the influence of quantum effects on the proton's position in the hydrogen bridge. In addition, quantum effects were incorporated a posteriori into calculations of O-H stretching envelopes for the Schiff and Mannich bases. Proton potential snapshots were extracted from the ab initio molecular dynamics trajectory. Vibrational Schrödinger equations (one- and two-dimensional) were solved numerically for the snapshots, and the O-H stretching envelopes were calculated as a superposition of the 0→1 transitions. Subsequently, one- and two-dimensional potentials of mean force (1D and 2D pmf) were calculated for the proton stretching mode from the proton vibrational eigenfunctions and eigenvalues incorporating statistical sampling and nuclear quantum effects. The results show that the applied methodologies are in good agreement with experimental infrared spectra. Additionally, it is demonstrated that the 2D pmf method could be applied in systems with strong anharmonicity to describe the properties of the O-H stretching mode more accurately. Future applications of the 2D pmf technique include, in principle, large biomolecular systems treated within the QM/MM framework.

  12. Dynamic analysis of polymeric fluid in shear flow for dumbbell model with internal viscosity

    Institute of Scientific and Technical Information of China (English)

    杨晓东; R.V.N.MELNIK

    2008-01-01

    The dynamic analysis of semi-flexible polymers,such as DNA molecules,is an important multiscale problem with a wide range of applications in science and bioengineering.In this contribution,a dumbbell model with internal viscosity was studied in steady shear flows of polymeric fluid.The tensors with moments other than second moment were approximated in the terms of second moment tensor.Then,the nonlinear algebraic equation of the second moment conformation tensor was calculated in closed form.Finally,substituting the resulting conformation tensor into the Kramers equation of Hookean spring force,the constitutive equations were obtained.The shear material properties were discussed for different internal viscosities and compared with the results of Brownian dynamics simulation.

  13. Internal resonances and dynamic responses in equivalent mechanical model of partially liquid-filled vessel

    Science.gov (United States)

    Farid, M.; Gendelman, O. V.

    2016-09-01

    The paper treats dynamical responses in an equivalent mechanical model for oscillations of a liquid in partially filled vessel under horizontal harmonic ground excitation. Such excitation may lead to hydraulic impacts. The liquid sloshing mass is modeled by equivalent pendulum, which can impact the vessel walls. Parameters of the equivalent pendulum for well-explored case of cylindrical vessels are used. The hydraulic impacts are modeled by high-power potential function. Conditions for internal resonances are formulated. A non-resonant behavior and dynamic response related to 3:1 internal resonance are explored. When the excitation amplitude exceeds certain critical value, the system exhibits multiple steady state solutions. Quasi-periodic solutions appear in relatively narrow range of parameters. Numerical continuation links between resonant regimes found asymptotically for small excitation amplitude, and high-amplitude responses with intensive impacts.

  14. Comparison of Standard Issue and ANCRA International MILVAN Restraint Beams in Static and Dynamic Environments

    Science.gov (United States)

    1990-04-01

    BEAMS IN STATIC AND DYNAMIC ENVIRONMENTS 93-10168 Prepared fo r: 1 8Distribution unlimited U.S. Army Troop Support Command ATTN: AMSTR-PLBM St. Louis ...ACCESSION NO St. Louis , MO 63120-1798 N 11 TITLE (Include Security Classification) Comparison of Standard Issue and ANCRA International MILVAN Restraint Beams...j * .** 4 ...*.**.*.* ... .* ***.***..***..*** 4-q14 drax @TO 31 aDlu \\t-I ur ne 4-1 r! S.......... .. •o

  15. The dynamics of internal tidal waves in Todos Santos Bay, Baja California, during experiment FLOO-2007

    Science.gov (United States)

    Filonov, A.; Lavin, M. F.; Ladah, L. B.; Tereshchenko, I.

    2012-04-01

    The aim of this work is to describe the characteristics of internal waves in Todos Santos Bay, Baja California (Mexico) from direct measurements made during the international experiment Fluxes Linking the Offshore with the Onshore (FLOO), which was held in August 2007. Time series of temperature and currents were obtained in the study area, placing several submerged moorings with chains of HOBO-V2 sensors and an ADCP. In addition, transects were made using a towed undulating CTD system and chains of thermographs which had a response time of 5 s. These measurements allowed the construction of the scenarios of generation, propagation and disintegration of the internal tide in the Bay. The internal tidal waves are generated by the barotropic tide at the edge of the continental shelf north of the Bay, have wavelengths ~9 km, are distributed in the form of an arc, and travel to the southeast with phase velocity ~20 cm/s . In shallow waters near the coast, tidal waves are refracted and quickly divide into groups of short nonlinear internal waves with amplitudes 15-20 m, periods 5-20 minutes, and wavelengths 50-200 m. Nonlinear internal waves play an important role in the dynamics of Todos Santos Bay, especially in the coastal zone. During partial or total destruction, vertical mixing and sudden changes of stratification take place. This affects the formation of the vertical structure of water density and ocean biological productivity.

  16. 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.

  17. 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.

  18. Nonlinear dynamics of hidden modes in a system with internal symmetry

    Science.gov (United States)

    Perchikov, Nathan; Gendelman, O. V.

    2016-09-01

    We consider a discrete dynamical system with internal degrees of freedom (DOF). Due to the symmetry between the internal DOFs, certain internal modes cannot be excited by external forcing (in a case of linear interactions) and thus are considered "hidden". If such a system is weakly asymmetric, the internal modes remain approximately "hidden" from the external excitation, given that small damping is taken into account. However, already in the case of weak cubic nonlinearity, these hidden modes can be excited, even as the exact symmetry is preserved. This excitation occurs through parametric resonance. Floquet analysis reveals instability patterns for the explored modes. To perform this analysis with the required accuracy, we suggest a special method for obtaining the Fourier series of the unperturbed solution for the nonlinear normal mode. This method does not require explicit integration of the arising quadratures. Instead, it employs expansion of the solution at the stage of the implicit quadrature in terms of Chebyshev polynomials. The emerging implicit equations are solved by using a fixed-point iteration scheme. Poincaré sections help to clarify the correspondence between the loss of stability of the modes and the global structure of the dynamical flow. In particular, the conditions for intensive energy exchange in the system are characterized.

  19. 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

    Hydrodynamic stability is of fundamental importance in fluid dynamics. As a well-established subject of scientific investigation, it continues to attract great interest in the fluid mechanics community. Bifurcations and instabilities are observed in all areas of fundamental and applied fluid...... 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...... International Symposium on Instability and Bifurcations in Fluid Dynamics (BIFD) held at the ESPCI, Paris, 15–17 July2015. With four invited and nearly 400 contributed talks, the symposium gave an overview of the state of the art of the field including experimental, theoretical, and computational approaches...

  20. Intramolecular bond length dependence of the anisotropic dispersion coefficients for H2-rare gas interactions

    Science.gov (United States)

    Wormer, Paul E. S.; Hettema, Hinne; Thakkar, Ajit J.

    1993-05-01

    Effective states arising from variational perturbation calculations in a full configuration interaction basis are used to calculate dynamic multipole polarizabilities for H2 at seven different bond lengths. These are combined with previously calculated dynamic polarizabilities for rare gas atoms to obtain the intramolecular bond length dependence of the anisotropic C6, C8, and C10 dispersion coefficients for H2-X (X=He, Ne, Ar, Kr, Xe) interactions. The results are generally in good agreement with previous semiempirical estimates where available.

  1. Effects of a naturally occurring compatible osmolyte on the internal dynamics of ribonuclease A.

    Science.gov (United States)

    Wang, A; Robertson, A D; Bolen, D W

    1995-11-21

    Osmolytes are small organic solutes accumulated intracellularly by many organisms as they adapt to environmental stresses. Compatible osmolytes, a functional class of osmolytes, increase protein stability while having little or no effect on protein function. To investigate the interrelationships between protein stability, function, and internal dynamics, a hydrogen exchange (HX) quench method was established and used to study the effects of sucrose (a typical compatible osmolyte) on the structural fluctuations of ribonuclease A. It was found that the HX rates of the amide protons with intermediate rates are not affected by 1 M sucrose, but the slow-exchanging amide protons exchange even slower in 1 M sucrose. The protection factors of the slow-exchanging protons fall into a comparatively narrow range while those of the intermediate-exchanging protons vary widely. In agreement with the two-process model [Woodward, C.K., & Hilton, B. D. (1980) Biophys. J. 32, 561-575], we conclude that for those slow-exchanging amide protons, the exchange occurs mainly from the compact unfolded state ensemble of the protein. The internal dynamics leading to slow exchange involve exposure of large protein surface areas, similar to that which occurs upon the unfolding of protein. Because sucrose opposes such an increase in protein surface area exposure, both the slow HX rates and the protein stability are affected by sucrose. For those amide protons with fast and intermediate HX rates, the exchange occurs mainly from the native state ensemble of the protein. The internal dynamics involved in the exchange are localized without much surface area change, and functionally important structural fluctuations are likely to occur within this dynamic range.(ABSTRACT TRUNCATED AT 250 WORDS)

  2. Intramolecular electron transfer in Pseudomonas aeruginosa cd(1) nitrite reductase

    DEFF Research Database (Denmark)

    Farver, Ole; Brunori, Maurizio; Cutruzzolà, Francesca

    2009-01-01

    nitrite reductase has been determined in both fully oxidized and reduced states. Intramolecular electron transfer (ET), between c and d(1) hemes is an essential step in the catalytic cycle. In earlier studies of the Pseudomonas stutzeri enzyme, we observed that a marked negative cooperativity......The cd(1) nitrite reductases, which catalyze the reduction of nitrite to nitric oxide, are homodimers of 60 kDa subunits, each containing one heme-c and one heme-d(1). Heme-c is the electron entry site, whereas heme-d(1) constitutes the catalytic center. The 3D structure of Pseudomonas aeruginosa......-controlled bimolecular process, followed by unimolecular electron equilibration between the c and d(1) hemes (k(ET) = 4.3 s(-1) and K = 1.4 at 298 K, pH 7.0). In the case of the mutant, the latter ET rate was faster by almost one order of magnitude. Moreover, the internal ET rate dropped (by approximately 30-fold...

  3. The Dynamics of Internalizing and Externalizing Comorbidity Across the Early School Years

    Science.gov (United States)

    Willner, Cynthia J.; Gatzke-Kopp, Lisa M.; Bray, Bethany C.

    2017-01-01

    High rates of comorbidity are observed between internalizing and externalizing problems, yet the developmental dynamics of comorbid symptom presentations are not yet well understood. This study explored the developmental course of latent profiles of internalizing and externalizing symptoms across kindergarten, 1st, and 2nd grade. The sample consisted of 336 children from an urban, low-income community, selected based on relatively high (61%) or low (39%) aggressive/oppositional behavior problems at school entry (64% male; 70% African American, 20% Hispanic). Teachers reported on children’s symptoms in each year. An exploratory latent profile analysis of children’s scores on aggression/oppositionality, hyperactivity/inattention, anxiety, and social withdrawal symptom factors revealed 4 latent symptom profiles: comorbid (48% of the sample in each year), internalizing (19–23%), externalizing (21–22%), and well-adjusted (7–11%). The developmental course of these symptom profiles was examined using a latent transition analysis, which revealed remarkably high continuity in the comorbid symptom profile (89% from one year to the next) and moderately high continuity in both the internalizing and externalizing profiles (80% and 71%, respectively). Internalizing children had a 20% probability of remitting to the well-adjusted profile by the following year, whereas externalizing children had a 25% probability of transitioning to the comorbid profile. These results are consistent with the hypothesis that a common vulnerability factor contributes to developmentally stable internalizing-externalizing comorbidity, while also suggesting that some children with externalizing symptoms are at risk for subsequently accumulating internalizing symptoms. PMID:27739391

  4. Intramolecular epitope spreading in Heymann nephritis.

    Science.gov (United States)

    Shah, Pallavi; Tramontano, Alfonso; Makker, Sudesh P

    2007-12-01

    Immunization with megalin induces active Heymann nephritis, which reproduces features of human idiopathic membranous glomerulonephritis. Megalin is a complex immunological target with four discrete ligand-binding domains (LBDs) that may contain epitopes to which pathogenic autoantibodies are directed. Recently, a 236-residue N-terminal fragment, termed "L6," that spans the first LBD was shown to induce autoantibodies and severe disease. We used this model to examine epitope-specific contributions to pathogenesis. Sera obtained from rats 4 weeks after immunization with L6 demonstrated reactivity only with the L6 fragment on Western blot, whereas sera obtained after 8 weeks demonstrated reactivity with all four recombinant fragments of interest (L6 and LBDs II, III, and IV). We demonstrated that the L6 immunogen does not contain the epitopes responsible for the reactivity to the LBD fragments. Therefore, the appearance of antibodies directed at LBD fragments several weeks after the primary immune response suggests intramolecular epitope spreading. In vivo, we observed a temporal association between increased proteinuria and the appearance of antibodies to LBD fragments. These data implicate B cell epitope spreading in antibody-mediated pathogenesis of active Heymann nephritis, a model that should prove valuable for further study of autoimmune dysregulation.

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

    Science.gov (United States)

    Kandel, Saugat; Salomon-Ferrer, Romelia; Larsen, Adrien B; Jain, Abhinandan; Vaidehi, Nagarajan

    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

  6. 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

  7. The Role of Family Income Dynamics in Predicting Trajectories of Internalizing and Externalizing Problems.

    Science.gov (United States)

    Miller, Portia; Votruba-Drzal, Elizabeth

    2017-04-01

    Economic disparities in children's behavioral functioning have been observed in prior research. Yet, studies have ignored important perspectives from developmental psychopathology and have not delineated how aspects of income dynamics (i.e., cumulative family income versus income volatility) differentially relate to behavior problems. To address these limitations, the current study examined how both cumulative income and income volatility predict trajectories of children's internalizing and externalizing problems from kindergarten through fifth grade in a nationally representative sample of 10,900 children (51.4 % male). Results showed four distinct trajectories of internalizing problems and five distinct externalizing trajectories. Family income dynamics were related to trajectory group membership. Specifically, increased cumulative income decreased risk of membership in mid-increasing and mid-stable internalizing groups, and children whose families experienced multiple waves of income loss were 2.4 times as likely to be in the mid-increasing group instead of the low-stable group. With respect to externalizing, higher cumulative income increased the likelihood of belonging in the group exhibiting stably low externalizing problems. Experiencing income loss increased the risk of belonging in the trajectory group exhibiting chronically high externalizing behaviors. These results enhance our knowledge of the role of family income in the development of behavior problems.

  8. Dynamic MR imaging of internal derangements of the temporomandibular joint: correlation with clinical signs and symptoms

    Energy Technology Data Exchange (ETDEWEB)

    Cho, Young Ah; Chun, Eun Ju; Kim, Yoo Kyung; Yoo, Jeong Hyun; Choi, Hae Young; Kim, Hyun Jin [Ewha Womans Univ. College of Medicine, Seoul (Korea, Republic of); Chung, Eun Chul [Sungkyunkwan Univ. College of Medicine, Seoul (Korea, Republic of)

    1999-01-01

    To evaluate the correlation between findings of dynamic magnetic resonance (MR) imaging of the temporomandibular joint (TMJ) and clinical findings in patients with internal derangement of the TMJ. Dynamic MR images of 130 joints of 65 patients (17 men and 48 women aged 14 to 74; mean age, 34) with internal derangement of the TMJ were obtained using a 1.5-T MR imaging system. MR findings of anterior displacement, disc deformity and degenerative change were correlated with clinical findings including joint pain, clicking sound, crepitation and maximal mouth opening (MMO). Among 62 joints with TMJ pain, 32 showed anterior displacement without reduction, 15 showed disc deformity and 19 showed degenerative change. Among 49 joints in which there was a clicking sound, 24, 8 and 12 joints, respectively, showed the above-mentioned findings, while in seven with crepitation, these same findings were evident in five, six and four joints, respectively. Bilateral and unilateral joint disorders were observed in 17 and five patients, respectively, among 22 with MMO less than 30mm and in 11 and 18 of 42 patients with MMO between 30mm and 60mm. On MR imaging, patients with MMO less than 30mm usually showed bilateral joint disorders and those with crepitation showed chronic change. This indicates that there is high association between clinical findings of internal derangement of TMJ and MR findings.

  9. 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.

  10. Asymmetric Intramolecular Cyclopropanation Induced by (β-Diketone)-copper Complex

    Institute of Scientific and Technical Information of China (English)

    Qing Fang CHENG; Xing You XU; Wei Xing MA; Tian Pa YOU

    2005-01-01

    Asymmetric intramolecular cyclopropanation of allylic diazoacetate was investigated using a chiral (β-diketone)-copper complex as catalyst, excellent yield and enantioselectivity were achieved. Some factors influencing enantioselectivity were discussed.

  11. 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.

  12. 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

  13. Novel Intramolecular Coordination Chemistry of Some New Metallocene Complexes

    Institute of Scientific and Technical Information of China (English)

    钱延龙; 黄吉玲

    2001-01-01

    This article summarizes the recent results of systematic study on the novel intramolecular cordination chemistry of some new substituted metallocene complexes made by our research group.It deals with the syntheses,reactions,structures of 65 new substituted metallocene complexes and some application of such coordination in homogeneous ctalysis,especially the structural chemistry of such novel intramolecular coordination complexes,and the mechanism of elimination and cyclization of such coordination compounds,as well as their control action in catalytic reactions.

  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. Internal and external dynamics in language: Evidence from verb regularity in a historical corpus of English

    CERN Document Server

    Cuskley, Christine F; 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 irr...

  16. Internal resonances and dynamic responses in equivalent mechanical model of partially liquid-filled vessel

    CERN Document Server

    Farid, Maor

    2016-01-01

    The paper treats oscillations of a liquid in partially filled vessel under horizontal harmonic ground excitation. Such excitation may lead to hydraulic impacts. The liquid sloshing mass is modeled by equivalent pendulum, which can impact the vessel walls. We use parameters of the equivalent pendulum for well-explored case of cylindrical vessels. The hydraulic impacts are modeled by high-power potential function. Conditions for internal resonances are presented. A non-resonant behavior and dynamic response related to 3:1 internal resonance are explored. When the excitation amplitude exceeds a critical value, the system exhibits multiple steady state solutions. Quasi-periodic solutions appear in relatively narrow range of parameters. Numerical continuation links between resonant regimes found asymptotically for small excitation amplitude, and high-amplitude responses with intensive impacts.

  17. 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.

  18. Attitude Dynamics of a Spinning Rocket with Internal Fluid Whirling Motion

    Directory of Open Access Journals (Sweden)

    Marius Ionut MARMUREANU

    2014-06-01

    Full Text Available This paper evaluates the impact that helical motion of fluid products of combustion within the combustion chamber of a rocket can have on the attitude dynamics of rocket systems. By developing the study presented by Sookgaew (2004, we determined the configuration of the Coriolis moment components, which catch the impact of the combustion product’s whirling motion, for the radial and centripetal propellant burn pattern specific to S-5M and S-5K solid rocket motors. We continue the investigation of the effects of internal whirling motion of fluid products of combustion on the attitude behavior of variable mass systems of the rocket type by examining the spin motion and transverse attitude motion of such systems. The results obtained show that internal fluid whirling motion can cause appreciable deviations in spin rate predictions, and also affects the frequencies of the transverse angular velocity components.

  19. Nonlinear dynamic behaviors of clamped laminated shallow shells with one-to-one internal resonance

    Science.gov (United States)

    Abe, Akira; Kobayashi, Yukinori; Yamada, Gen

    2007-07-01

    This paper investigates one-to-one internal resonance of laminated shallow shells with rigidly clamped edges. It is assumed that the natural frequencies ω2 and ω3 of two asymmetric (second and third) vibration modes have the relationship ω2≈ ω3. The displacements are expressed by using eigenvectors for linear vibration modes calculated by the Ritz method. Applying Galerkin's procedure to the equation of motion, nonlinear differential equations are derived. By considering the first vibration mode in addition to the two asymmetric vibration modes, quadratic nonlinear terms expressing the interaction between the asymmetric and the first modes appear in the differential equations. Shooting method is used to obtain the steady-state response when the driving frequency Ω is near ω2. The dynamic characteristics of the shells with the internal resonance are discussed.

  20. Development of an internal dynamic web site to promote quality assurance in a clinical laboratory.

    Science.gov (United States)

    Pernet, Pascal; Mario, Nathalie; Vaubourdolle, Michel

    2004-01-01

    In clinical laboratories, one challenging quality assurance objective is to maintain standardized practices. Meeting this objective entails ensuring information flow, which is necessary to smooth running of the laboratory. To facilitate information flow, we developed an internal quality Web site on our local network. The dynamic generated pages of the site were constructed with EasyPHP v.1.6, a complete freeware package providing PHP dynamic language and databases. The site comprises various sections: general news, specific laboratory units news, documents (quality manual, guidelines, emergency processes), schedules, National Quality Control results, forum, etc. Five to 10 pages are updated each week. This work was facilitated by the use of PHP-written pages and data tables, which enable us to record in real time the operation of our assurance quality project and to improve traceability. This approach could be extended to other aspects of quality management and could help meet the future IS015189 standard requirements.

  1. External and internal gelation of pectin solutions: microscopic dynamics versus macroscopic rheology

    Science.gov (United States)

    Secchi, E.; Munarin, F.; Alaimo, M. D.; Bosisio, S.; Buzzaccaro, S.; Ciccarella, G.; Vergaro, V.; Petrini, P.; Piazza, R.

    2014-11-01

    Pectin is a natural biopolymer that forms, in the presence of divalent cations, ionic-bound gels typifying a large class of biological gels stabilized by non-covalent cross-links. We investigate and compare the kinetics of formation and aging of pectin gels obtained either through external gelation via perfusion of free Ca2+ ions, or by internal gelation due to the supply of the same ions from the dissolution of CaCO3 nanoparticles. The microscopic dynamics obtained with photon correlation imaging, a novel optical technique that allows obtaining the microscopic dynamics of the sample while retaining the spatial resolution of imaging techniques, is contrasted with macroscopic rheological measurements at constant strain. Pectin gelation is found to display peculiar two-stage kinetics, highlighted by non-monotonic growth in time of both microscopic correlations and gel mechanical strength. These results are compared to those found for alginate, another biopolymer extensively used in food formulation.

  2. External and internal gelation of pectin solutions: microscopic dynamics versus macroscopic rheology.

    Science.gov (United States)

    Secchi, E; Munarin, F; Alaimo, M D; Bosisio, S; Buzzaccaro, S; Ciccarella, G; Vergaro, V; Petrini, P; Piazza, R

    2014-11-19

    Pectin is a natural biopolymer that forms, in the presence of divalent cations, ionic-bound gels typifying a large class of biological gels stabilized by non-covalent cross-links. We investigate and compare the kinetics of formation and aging of pectin gels obtained either through external gelation via perfusion of free Ca(2+) ions, or by internal gelation due to the supply of the same ions from the dissolution of CaCO3 nanoparticles. The microscopic dynamics obtained with photon correlation imaging, a novel optical technique that allows obtaining the microscopic dynamics of the sample while retaining the spatial resolution of imaging techniques, is contrasted with macroscopic rheological measurements at constant strain. Pectin gelation is found to display peculiar two-stage kinetics, highlighted by non-monotonic growth in time of both microscopic correlations and gel mechanical strength. These results are compared to those found for alginate, another biopolymer extensively used in food formulation.

  3. The Figure and Dynamical Parameters of Io Inferred from Internal Structure Models

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    The recent Galileo spacecraft explored Jupiter and its satellite system and provided us with new geodetic data. In order to discuss the dynamical param-eters and secular tidal effect of Io, the theory of synchronous satellite is described in detail. Using the new geodetic data of Io, two sets of Io's internal structure models are constructed based on the asthenosphere assumption. The liberation parameters α, β, γ and dynamical flattening H are calculated for the models of Io.A comparison of Io with the Moon indicates that they are quite different in many characteristics in spite of the fact that they are approximately equal in mass and size and that they both orbit synchronously.

  4. Complex dynamics of functionally graded plates with thermal load in 1:2 internal resonance

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    Complex dynamics of the simply-supported functionally graded(FG)rectangular plates with thermal load is investigated.Based on Reddy’s third-order shear deformation theory and the von Karman nonlinear strain-displacement relations,ordinary differential equations(ODEs)of the plate’s transversal oscillation are derived by using Hamilton’s principle and Galerkin’s approach.Solutions’classification of the equations in 1:2 internal resonance is analyzed.Particular results of a simplysupported aluminum-alumina rectangular FG plate are given.Effects of temperature and volume fraction on the responses’ stabilities are discussed.

  5. Internal character dictates phase transition dynamics between isolation and cohesive grouping

    CERN Document Server

    Manrique, Pedro D; Johnson, Neil F

    2015-01-01

    We show that accounting for internal character among interacting, heterogeneous entities generates rich phase transition behavior between isolation and cohesive dynamical grouping. Our analytical and numerical calculations reveal different critical points arising for different character-dependent grouping mechanisms. These critical points move in opposite directions as the population's diversity decreases. Our analytical theory helps explain why a particular class of universality is so common in the real world, despite fundamental differences in the underlying entities. Furthermore, it correctly predicts the non-monotonic temporal variation in connectivity observed recently in one such system.

  6. Understanding the internal dynamics of elliptical galaxies without non-baryonic dark matter

    CERN Document Server

    Dabringhausen, J; Famaey, B; Fellhauer, M

    2016-01-01

    Assuming virial equilibrium and Newtonian dynamics, low-mass early-type galaxies have larger velocity dispersions than expected from the amount of baryons they contain. The conventional interpretation of this finding is that their dynamics is dominated by non-baryonic matter. However, there is also strong evidence that many low-mass early-type galaxies formed as tidal dwarf galaxies, which would contain almost no dark matter. Using an extensive catalogue of early-type galaxies, we therefore discuss how the internal dynamics of early-type galaxies in general can be understood by replacing the assumption of non-baryonic dark matter with two alternative assumptions. The first assumption is that Milgromian dynamics (i.e., MOND) is valid, which changes the effective gravitational force in the weak-field limit. The second assumption is that binary stars affect the observed line-of-sight velocity dispersions. Some moderate discrepancies between observed and predicted velocity dispersions remain also when these effec...

  7. Dynamical and statistical effects of the intrinsic curvature of internal space of molecules.

    Science.gov (United States)

    Teramoto, Hiroshi; Takatsuka, Kazuo

    2005-02-15

    The Hamilton dynamics of a molecule in a translationally and/or rotationally symmetric field is kept rigorously constrained in its phase space. The relevant dynamical laws should therefore be extracted from these constrained motions. An internal space that is induced by a projection of such a limited phase space onto configuration space is an intrinsically curved space even for a system of zero total angular momentum. In this paper we discuss the general effects of this curvedness on dynamics and structures of molecules in such a manner that is invariant with respect to the selection of coordinates. It is shown that the regular coordinate originally defined by Riemann is particularly useful to expose the curvature correction to the dynamics and statistical properties of molecules. These effects are significant both qualitatively and quantitatively and are studied in two aspects. One is the direct effect on dynamics: A trajectory receives a Lorentz-like force from the curved space as though it was placed in a magnetic field. The well-known problem of the trapping phenomenon at the transition state is analyzed from this point of view. By showing that the trapping force is explicitly described in terms of the curvature of the internal space, we clarify that the physical origin of the trapped motion is indeed originated from the curvature of the internal space and hence is not dependent of the selection of coordinate system. The other aspect is the effect of phase space volume arising from the curvedness: We formulate a general expression of the curvature correction of the classical density of states and extract its physical significance in the molecular geometry along with reaction rate in terms of the scalar curvature and volume loss (gain) due to the curvature. The transition state theory is reformulated from this point of view and it is applied to the structural transition of linear chain molecules in the so-called dihedral angle model. It is shown that the

  8. 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

  9. 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

  10. 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.

  11. 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.

  12. Dynamics of surfactants in the field of edge and internal waves in coastal areas

    Science.gov (United States)

    Averbukh, L.; Kurkina, O.; Kurkin, A.

    2012-04-01

    Edge waves are topographically trapped waves, which can be considered as an important factor impacting upon coastline and nearshore bottom relief, beaches and coastal constructions. Large amplitude nonlinear edge waves are possible due to the action of different mechanisms. Their dynamics can be described by nonlinear Shrodinger equation, and the signs of its coefficients correspond to modulation instability of wave packets. The mechanisms of possible anomalous edge wave appearance are dispersion enhancement and self-modulation; they can lead to forming of abnormal edge wave. In the present paper we consider processes of edge wave propagation and amplification along a cylindrical shelf taking into account horizontal alongshore flow and Earth rotation. Internal waves exist in stratified coastal areas, and for them extreme regimes are also well-known, including propagation of such energetic events as solitary waves and breathers. The existence of waves of both type lead to formation of wave-induced currents, which can be quite strong and can significantly affect the surrounding environment. In particular, these currents can influence upon pollutants, admixtures and films on the surface of the sea causing their redistribution according to zones of convergence and divergence of the velocity fields. These specific pictures on the surface can be used in the interpretation of remote sensing data and diagnostics and identification of underlying wave processes. In the present study we demonstrate dynamics of surfactants in the field of edge and internal waves in coastal areas. Numerical modeling is based on the balance equation of the surface concentration. Film dynamics was considered in the advection - diffusion - relaxation model. We show a number of unsteady effects in the edge and internal waves and their manifestation in the surfactants. For edge waves we considered the passage of linear traveling and standing waves, the wave amplitude changes due to slow longshore

  13. Excited state intramolecular charge transfer reaction in 4-(1-azetidinyl)benzonitrile: Solvent isotope effects

    Indian Academy of Sciences (India)

    Tuhin Pradhan; Piue Ghoshal; Ranjit Biswas

    2009-01-01

    Excited state intramolecular charge transfer reaction of 4-(1-azetidinyl) benzonitrile (P4C) in deuterated and normal methanol, ethanol and acetonitrile has been studied in order to investigate the solvent isotope effects on reaction rates and yields. These quantities (reaction rates and yields) along with several other properties such as quantum yield and radiative rates have been found to be insensitive to the solvent isotope substitution in all these solvents. The origin of the solvent isotope insensitivity of the reaction is discussed and correlated with the observed slowing down of the solvation dynamics upon isotope substitution.

  14. 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.

  15. 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.

  16. Multi-loop adaptive internal model control based on a dynamic partial least squares model

    Institute of Scientific and Technical Information of China (English)

    Zhao ZHAO; Bin HU; Jun LIANG

    2011-01-01

    A multi-loop adaptive internal model control (IMC) strategy based on a dynamic partial least squares (PLS) framework is proposed to account for plant model errors caused by slow aging, drift in operational conditions, or environmental changes. Since PLS decomposition structure enables multi-loop controller design within latent spaces, a multivariable adaptive control scheme can be converted easily into several independent univariable control loops in the PLS space. In each latent subspace,once the model error exceeds a specific threshold, online adaptation rules are implemented separately to correct the plant model mismatch via a recursive least squares (RLS) algorithm. Because the IMC extracts the inverse of the minimum part of the internal model as its structure, the IMC controller is self-tuned by explicitly updating the parameters, which are parts of the internal model.Both parameter convergence and system stability are briefly analyzed, and proved to be effective. Finally, the proposed control scheme is tested and evaluated using a widely-used benchmark of a multi-input multi-output (MIMO) system with pure delay.

  17. No effect of covalently linked poly(ethylene glycol) chains on protein internal dynamics.

    Science.gov (United States)

    Gonnelli, Margherita; Strambini, Giovanni B

    2009-03-01

    Poly(ethylene glycol) or PEG is a hydrophilic polymer that covalently linked to therapeutical proteins may significantly increase their pharmacological properties. Despite the extensive production of PEG-conjugated proteins the effects of the polymer on the protein structure and dynamics is poorly understood, making the production of active biomaterials a largely unpredictable process. The present investigation examines the effects of 5 k and 20 k PEG on the internal flexibility of Ribonuclease T1, the mutant C112S of azurin from Pseudomonas aeruginosa, alcohol dehydrogenase and alkaline phosphatase, native and Zn-depleted. These systems encompass structural domains that range from rather superficial, flexible sites to deeply buried, rigid cores. The approach is based on three sensitive parameters related to the phosphorescence emission of internal Trp residues, namely, the intrinsic room-temperature phosphorescence lifetime (tau(0)) that reports on the local flexibility of the protein matrix around the chromophore and the bimolecular rate constant (k(q)) for the quenching of phosphorescence by O(2) and by acrylamide in solution, which are related to the diffusion of these solutes through the protein fold. The results obtained by these three independent, intrinsic probes of protein structure-dynamics concur that mono-PEGylation does not detectably perturb the conformation and dynamics of the protein native fold, over a wide temperature range. The implication is that protein motions are essentially not coupled to the polymer and that adverse effects of chemical modification on biological function are presumably owed to steric hindrance by PEG units blocking the access to sites critical for molecular recognition.

  18. Binaries traveling through a gaseous medium: Dynamical drag forces and internal torques

    CERN Document Server

    Sanchez-Salcedo, F J

    2014-01-01

    Using time-dependent linear theory, we investigate the morphology of the gravitational wake induced by a binary, whose center of mass moves at velocity Vcm against a uniform background of gas. For simplicity, we assume that the binary's components are on circular orbits about their common center of mass. The consequences of dynamical friction is twofold. First, gas dynamical friction may drag the binary's center of mass and cause the binary to migrate. Second, drag forces also induce a braking torque, which causes the orbits of the binary components 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 to decelerate the binary's center of mass 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 numbe...

  19. Structure and Evolution of Galaxy Clusters Internal Dynamics of ABCG 209 at z~0.21

    CERN Document Server

    Mercurio, A; Boschin, W; Merluzzi, P; Busarello, G

    2003-01-01

    We study the internal dynamics of the rich galaxy cluster ABGC 209 on the basis of new spectroscopic and photometric data. The distribution in redshift shows that ABCG 209 is a well isolated peak of 112 detected member galaxies at z=0.209, characterised by a high value of the line-of-sight velocity dispersion, sigma_v=1250-1400 Km/s, on the whole observed area (1 Mpc/h from the cluster center), that leads to a virial mass of M=1.6-2.2x10^15 M_sun within the virial radius, assuming the dynamical equilibrium. The presence of a velocity gradient in the velocity field, the elongation in the spatial distribution of the colour-selected likely cluster members, the elongation of the X-ray contour levels in the Chandra image, and the elongation of cD galaxy show that ABCG 209 is characterised by a preferential NW-SE direction. We also find a significant deviation of the velocity distribution from a Gaussian, and relevant evidence of substructure and dynamical segregation. All these facts show that ABCG 209 is a strong...

  20. Humeral elevation reduces the dynamic control ratio of the shoulder muscles during internal rotation.

    Science.gov (United States)

    Howard, William; Burgess, Jonathan; Vrhovnik, Borut; Stringer, Christian; Choy, Sherrie T; Marsden, Jonathan F; Gedikoglou, Ingrid A; Shum, Gary L

    2017-04-01

    To determine the differences in the dynamic control ratio of the glenohumeral joint rotators, during internal rotation at 20° and 60° of humeral elevation in the scapular plan. Dynamic control ratio (DCR) is defined as the ratio between eccentric action of the lateral rotators and the concentric action of the medial rotators. A cross-sectional laboratory study. Thirty asymptomatic participants (men n=14, women n=16, mean age=29.4±8.9years, BMI: 24.1±5.4) were tested. Peak torque generated by the concentric action of the MR and the eccentric action of the LR of the shoulder joint and the DCR were evaluated on the dominant arm using an isokinetic dynamometer at 20° and 60° of humeral elevation at a speed of 20°/s. There was a significant decrease in the DCR at 60° humeral elevation when compared to 20° humeral elevation (p0.05). The significant decrease in the DCR as a consequence of a decrease in the eccentric peak torque of the LR when the humerus is in a more elevated position suggests that the introduction of humeral elevation can be used as a progression for improving the eccentric action of the shoulder LR and subsequently the dynamic control of the shoulder. Copyright © 2016 Sports Medicine Australia. Published by Elsevier Ltd. All rights reserved.

  1. Two New Methods To Generate Internal Coordinates for Molecular Wave Packet Dynamics in Reduced Dimensions.

    Science.gov (United States)

    Zauleck, Julius P P; Thallmair, Sebastian; Loipersberger, Matthias; de Vivie-Riedle, Regina

    2016-12-13

    The curse of dimensionality still remains as the central challenge of molecular quantum dynamical calculations. Either compromises on the accuracy of the potential landscape have to be made or methods must be used that reduce the dimensionality of the configuration space of molecular systems to a low dimensional one. For dynamic approaches such as grid-based wave packet dynamics that are confined to a small number of degrees of freedom this dimensionality reduction can become a major part of the overall problem. A common strategy to reduce the configuration space is by selection of a set of internal coordinates using chemical intuition. We devised two methods that increase the degree of automation of the dimensionality reduction as well as replace chemical intuition by more quantifiable criteria. Both methods reduce the dimensionality linearly and use the intrinsic reaction coordinate as guidance. The first one solely relies on the intrinsic reaction coordinate (IRC), whereas the second one uses semiclassical trajectories to identify the important degrees of freedom.

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

    Directory of Open Access Journals (Sweden)

    Felea Adrian Ioan

    2015-07-01

    Full Text Available 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 competitiveness, especially the industrial competitiveness. Our country has an obvious deficit regarding the international trade balance and thus the analysis of this subject is very relevant at a sectorial level and at national economy’s branches level, when identifying solutions for raising the competitiveness. This paper is dedicated to studying Romania’s industrial competitiveness analysis throughout the recent values of the imports and exports, generated by the industry and its branches. After identifying this concern utility, this article presents the methodology used, defining and experiencing the indicators proposed for characterising the level of industrial competitiveness and also the level and dynamic of the industrial trade. In the practical part of this paper, we presented the recent evolution of the values of imports and exports for the industrial products, the share of industrial sectors in the international trade balance, particularizing the manufacturing industry – the most important industrial sector – at branch level. In the analysis of the manufacturing industry we proposed a classifying methodology divided in six levels of competitiveness, associating and characterizing the branches. The conclusions present the possible solutions for improving the Romanian international industrial trade balance.

  3. 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

  4. The fluorescence and dynamics properties in phenoxy-phthalocyanines liquid

    Science.gov (United States)

    Yao, Cheng-Bao; Yan, Xiao-Yan; Tan, Ming-Yue; Li, Jin; Sun, Wen-Jun; Yang, Shou-Bin

    2015-06-01

    We investigated the one/two-photon fluorescence and excited state dynamics properties of two synthesized phenoxy-phthalocyanines (Pc1 and Pc2) using mild reaction coordination method. The results show that the fast decay component in the time-resolved fluorescence technique dynamics comes from the intramolecular vibrational relaxation, the slower ones from the internal conversion. Furthermore, in comparison with one-photon fluorescence spectra, the red shift of two-photon fluorescence spectra can be explained by the reabsorption effect of molecules. The samples are expected to be a potential candidate for optical applications and photodynamic therapy.

  5. Tropical Pacific internal atmospheric dynamics and resolution in a coupled GCM

    Science.gov (United States)

    Lopez, Hosmay; Kirtman, Ben P.

    2015-01-01

    A noise reduction technique, namely the interactive ensemble (IE) approach is adopted to reduce noise at the air-sea interface due to internal atmospheric dynamics in a state-of-the-art coupled general circulation model (CGCM). The IE technique uses multiple realization of atmospheric general circulation models coupled to a single ocean general circulation model. The ensembles mean fluxes from the atmospheric simulations are communicated to the ocean component. Each atmospheric simulation receives the same SST coming from the ocean component. The only difference among the atmospheric simulations comes from perturbed initial conditions, thus the atmospheric states are, in principle synoptically independent. The IE technique can be used to better understand the importance of weather noise forcing of natural variability such as El Niño Southern Oscillation (ENSO). To study the impact of weather noise and resolution in the context of a CGCM, two IE experiments are performed at different resolutions. Atmospheric resolution is an important issue since the noise statistics will depend on the spatial scales resolved. A simple formulation to extract atmospheric internal variability is presented. The results are compared to their respective control cases where internal atmospheric variability is left unchanged. The noise reduction has a major impact on the coupled simulation and the magnitude of this effect strongly depends on the horizontal resolution of the atmospheric component model. Specifically, applying the noise reduction technique reduces the overall climate variability more effectively at higher resolution. This suggests that "weather noise" is more important in sustaining climate variability as resolution increases. ENSO statistics, dynamics, and phase asymmetry are all modified by the noise reduction, in particular ENSO becomes more regular with less phase asymmetry when noise is reduced. All these effects are more marked for the higher resolution case. In

  6. Donor-Acceptor Conjugated Linear Polyenes: A Study of Excited State Intramolecular Charge Transfer, Photoisomerization and Fluorescence Probe Properties.

    Science.gov (United States)

    Hota, Prasanta Kumar; Singh, Anil Kumar

    2014-07-27

    Numerous studies of donor-acceptor conjugated linear polyenes have been carried out with the goal to understand the exact nature of the excited state electronic structure and dynamics. In this article we discuss our endeavours with regard to the excited state intramolecular charge transfer, photoisomerization and fluorescence probe properties of various donor-acceptor substituted compounds of diphenylpolyene [Ar(CH = CH) n Ar] series and ethenylindoles.

  7. PREFACE: International Conference on Dynamics of Systems on the Nanoscale (DySoN 2012)

    Science.gov (United States)

    Solov'yov, Andrey V.

    2013-06-01

    Conference logo The Second International Conference 'Dynamics of Systems on the Nanoscale' (DySoN 2012) took place in Saint Petersburg, Russia between 30 September and 4 October 2012. The venue was the Courtyard by Marriott St Petersburg Vasilievsky Hotel, 2nd line of Vasilievsky Island 61/30A, 199178. The conference was organized by the Frankfurt Institute for Advanced Studies - Goethe University, A F Ioffe Physical-Technical Institute and Saint Petersburg State Polytechnic University. This DySoN conference has been built upon a series of International Symposia 'Atomic Cluster Collisions: structure and dynamics from the nuclear to the biological scale' (ISACC 2003, ISACC 2007, ISACC 2008, ISACC 2009 and ISACC 2011). During these meetings it has become clear that there is a need for an interdisciplinary conference covering a broader range of topics than just atomic cluster collisions, related to the Dynamics of Systems on a Nanoscale. Therefore, in 2010 it was decided to launch a new conference series under the title 'Dynamics of Systems on the Nanoscale'. The first DySoN conference took place at the National Research Council, Rome, Italy in 2010. The DySoN 2012 is the second conference in this series. The DySoN 2012 Conference promoted the growth and exchange of interdisciplinary scientific information on the structure, formation and dynamics of animate and inanimate matter on the nanometer scale. There are many examples of complex many-body systems of micro- and nanometer scale size exhibiting unique features, properties and functions. These systems may have very different nature and origin, e.g. atomic and molecular clusters, nanoobjects, ensembles of nanoparticles, nanostructures, biomolecules, biomolecular and mesoscopic systems. A detailed understanding of the structure and dynamics of these systems on the nanometer scale is an important fundamental task, the solution of which is necessary in numerous applications of nano- and biotechnology, material science

  8. Numerical simulation of a direct internal reforming solid oxide fuel cell using computational fluid dynamics methodas

    Institute of Scientific and Technical Information of China (English)

    Jun LI; Ying-wei KANG; Guang-yi CAO; Xin-jian ZHU; Heng-yong TU; Jian LI

    2008-01-01

    A detailed mathematical model of a direct internal reforming solid oxide fuel cell (DIR-SOFC) incorporating with simulation of chemical and physical processes in the fuel cell is presented. The model is developed based on the reforming and electrochemical reaction mechanisms, mass and energy conservation, and heat transfer. A computational fluid dynamics (CFD) method is used for solving the complicated multiple partial differential equations (PDEs) to obtain the numerical approximations.The resulting distributions of chemical species concentrations, temperature and current density in a cross-flow DIR-SOFC are given and analyzed in detail. Further, the influence between distributions of chemical species concentrations, temperature and current density during the simulation is illustrated and discussed. The heat and mass transfer, and the kinetics of reforming and electrochemical reactions have significant effects on the parameter distributions within the cell. The results show the particularchar acteristics of the DIR-SOFC among fuel cells, and can aid in stack design and control.

  9. An Application of Dynamic Programming Principle in Corporate International Optimal Investment and Consumption Choice Problem

    Directory of Open Access Journals (Sweden)

    Zongyuan Huang

    2010-01-01

    Full Text Available This paper is concerned with a kind of corporate international optimal portfolio and consumption choice problems, in which the investor can invest her or his wealth either in a domestic bond (bank account or in an oversea real project with production. The bank pays a lower interest rate for deposit and takes a higher rate for any loan. First, we show that Bellman's dynamic programming principle still holds in our setting; second, in terms of the foregoing principle, we obtain the investor's optimal portfolio proportion for a general maximizing expected utility problem and give the corresponding economic analysis; third, for the special but nontrivial Constant Relative Risk Aversion (CRRA case, we get the investors optimal investment and consumption solution; last but not least, we give some numerical simulation results to illustrate the influence of volatility parameters on the optimal investment strategy.

  10. Stability of Non-Neutral and Neutral Dynamic Switched Systems Subject to Internal Delays

    Directory of Open Access Journals (Sweden)

    M. De la Sen

    2005-01-01

    Full Text Available This study deals with the quadratic stability and linear state-feedback and output-feedback stabilization of switched delayed linear dynamic systems with, in general, a finite number of non commensurate constant internal point delays. The results are obtained based on Lyapunov’s stability analysis via appropriate Krasovsky-Lyapunov’s functionals and the related stability study is performed to obtain both delay independent and delay dependent results. It is proved that the stabilizing switching rule is arbitrary if all the switched subsystems are quadratically stable and that it exists a (in general, non-unique stabilizing switching law when the system is polytopic, stable at some interior point of the polytope but with non-necessarily stable parameterizations at the vertices defining the subsystems.

  11. 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.

  12. Dynamic neck development in a polymer tube under internal pressure loading

    DEFF Research Database (Denmark)

    Lindgreen, Britta; Tvergaard, Viggo; Needleman, Alan

    2008-01-01

    and a short wave length imperfection. After some thinning down at the necks, the mode of deformation switches to neck propagation along the circumference of the tube. A case is shown in which the necks have propagated along the entire tube wall, so that network locking in the polymer results in high stiffness......The initiation and growth of necks in polymer tubes subjected to rapidly increasing internal pressure is analyzed numerically. Plane strain conditions are assumed to prevail in the axial direction. The polymer is characterized by a finite strain elastic-viscoplastic constitutive relation...... and the calculations are carried out using a dynamic finite element program. Numerical results for neck development are illustrated and discussed for tubes of various thicknesses. The sensitivity to the wave number of the thickness imperfections is studied with a focus on comparing a long wave length imperfection...

  13. Lattice dynamics calculations for ferropericlase with internally consistent LDA+U method

    Science.gov (United States)

    Fukui, Hiroshi; Tsuchiya, Taku; Baron, Alfred Q. R.

    2012-12-01

    Vibrational densities of states and phonon dispersion relations for Mg0.875Fe0.125O ferropericlase in the high- and low-spin (HS and LS) states were calculated from first principles lattice dynamics using the internally consistent LDA+Utechnique. Finite-temperature thermodynamic properties were determined based on the quasi-harmonic approximation including the HS and LS mixing entropy and the magnetic entropy effects, which gave pressure and temperature variations of the low-spin fraction. Our results suggest that for thermodynamic modeling of the earth's interior, the effect of the mixed spin state cannot be ignored in the lower mantle, especially the lowermost part. The anomaly in the seismic wave velocity due to the spin crossover transition of ferropericlase, if it exists, is difficult to detect because of the wide pressure range of the transition, which is broadened by the temperature effect and the damping of the amplitude of the slow seismic wave.

  14. Photoinduced intramolecular charge transfer in push-pull polyenes: effects of solvation, electron-donor group, and polyenic chain length.

    Science.gov (United States)

    Akemann, Walther; Laage, Damien; Plaza, Pascal; Martin, Monique M; Blanchard-Desce, Mireille

    2008-01-17

    Subpicosecond absorption spectroscopy is used to characterize the primary photoinduced processes in a class of push-pull polyenes bearing a julolidine end group as the electron donor and a diethylthiobarbituric acid end group as the electron acceptor. The excited-state decay time and relaxation pathway have been studied for four polyenes of increasing chain length (n = 2-5 double bonds) in aprotic solvents of different solvation time, polarity, and viscosity. Intramolecular charge transfer (ICT) leading to a transient state of cyanine-like structure (fully conjugated with no bond length alternation) is observed in all polar solvents at a solvent dependent rate, but the reaction is not observed in cyclohexane, a nonpolar solvent. In polar solvents, the reaction time increases with the average solvation time but remains slightly larger, except in the viscous solvent triacetin. These facts are interpreted as an indication that both solvent reorganization and internal restructuring are involved in the ICT-state formation. The observed photodynamics resemble those we previously found for another class of polyenes bearing a dibutylaniline group as the donor, including a similar charge-transfer rate in spite of the larger electron donor character of the julolidine group. This observation brings further support to the proposal that an intramolecular coordinate is involved in the charge-transfer reaction, possibly a torsional motion of the donor end group. On the other hand, relaxation of the ICT state leads to cis-trans isomerization or crossing to the triplet state, depending on the length of the polyenic chain. In dioxane, tetrahydrofuran, and triacetin, the ICT state of the shorter chains (n = 2, 3) relaxes to the isomer with a viscosity-dependent rate, while that of the longer ones (n = 4, 5) leads to the triplet state with a viscosity-independent rate, as expected. In acetonitrile, the ICT-state lifetime is generally much shorter. A change from photoisomerization to

  15. Global analysis of fluorescence decays to probe the internal dynamics of fluorescently labeled macromolecules.

    Science.gov (United States)

    Duhamel, Jean

    2014-03-11

    The aim of this review is to introduce the reader first to the mathematical complexity associated with the analysis of fluorescence decays acquired with solutions of macromolecules labeled with a fluorophore and its quencher that are capable of interacting with each other via photophysical processes within the macromolecular volume, second to the experimental and mathematical approaches that have been proposed over the years to handle this mathematical complexity, and third to the information that one can expect to retrieve with respect to the internal dynamics of such fluorescently labeled macromolecules. In my view, the ideal fluorophore-quencher pair to use in studying the internal dynamics of fluorescently labeled macromolecules would involve a long-lived fluorophore, a fluorophore and a quencher that do not undergo energy migration, and a photophysical process that results in a change in fluorophore emission upon contact between the excited fluorophore and quencher. Pyrene, with its ability to form an excimer on contact between excited-state and ground-state species, happens to possess all of these properties. Although the concepts described in this review apply to any fluorophore and quencher pair sharing pyrene's exceptional photophysical properties, this review focuses on the study of pyrene-labeled macromolecules that have been characterized in great detail over the past 40 years and presents the main models that are being used today to analyze the fluorescence decays of pyrene-labeled macromolecules reliably. These models are based on Birks' scheme, the DMD model, the fluorescence blob model, and the model free analysis. The review also provides a step-by-step protocol that should enable the noneducated user to achieve a successful decay analysis exempt of artifacts. Finally, some examples of studies of pyrene-labeled macromolecules are also presented to illustrate the different types of information that can be retrieved from these fluorescence decay

  16. FOREWORD: Second International Symposium on Instability and Bifurcations in Fluid Dynamics

    Science.gov (United States)

    Bar Yoseph, P. Z.; Brøns, M.; Gelfgat, A.; Sørensen, J. N.

    2007-05-01

    Hydrodynamic stability is of fundamental importance in fluid dynamics and is a well-established subject of scientific investigation that continues to attract great interest in the fluid mechanics community. Hydrodynamic instabilities of prototypical character are, for example, the Rayleigh-Bénard, the Taylor-Couette, the Bénard-Marangoni, the Rayleigh-Taylor, and the Kelvin-Helmholtz instabilities. A fundamental understanding of various patterns of bifurcations such as identifying the most dominant mechanisms responsible for the instability threshold is also required if one is to design reliable and efficient industrial processes and applications, such as melting, mixing, crystal growth, coating, welding, flow re-attachment over wings, and others. The collection of papers in this volume is a selection of the presentations given at the Second International Symposium on Instability and Bifurcations in Fluid Dynamics, Technical University of Denmark, 15-18 August 2006. With more than 40 invited and contributed papers the symposium gave an overview of the state-of-the art of the field including experimental, theoretical, and computational approaches to problems related to convection, effects of magnetic fields, wake flows, rotating flows, and many others. The complete program can be found at the conference website http://www2.mat.dtu.dk/BIFD2006/. The symposium was the follow-up of a minisymposium held as a part of the `International Conference on Computational and Experimental Engineering and Sciences', 26-29 July 2004, Madeira, Portugal. We hope it will be possible to continue this series of highly successful events with a third symposium in 2008. P Z Bar Yoseph, M Brøns, A Gelfgat and J N Sørensen Editors

  17. Intermolecular and intramolecular electron transfer from eosin ester to viologen

    Institute of Scientific and Technical Information of China (English)

    张丰雷; 张曼华; 沈涛

    1996-01-01

    The covalently -(CH2)10- linked eosin-butylviologen compound has been synthesized. The photoinduced electron transfer of eosin ester and butylviologen as well as the influence of addition of cyclodextrin or amylose into the solution of linked compound on the system have been studied by the absorption spectra, fluorescence spectra and fluorescence lifetime. The results indicated that the intramolecular electron transfer is much more efficient than the intermolecular one. Due to the formation of inclusion complex, the process of intramolecular electron transfer was changed after adding cydodextrin or amylose.

  18. 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.

  19. Measurement of Young’s Modulus and Internal Damping of Pork Muscle in Dynamic Mode

    Science.gov (United States)

    Chakroun, Moez; Ghozlen, Med Hédi Ben

    2016-09-01

    Automotive shocks involve various tiers’ speed for different human body tissues. Knowing the behavior of these tissues, including muscles, in different vibration frequency is therefore necessary. The muscle has viscoelatic properties. Dynamically, this material has variable mechanical properties depending on the vibration frequency. A novel technique is being employed to examine the variation of the mechanical impedance of pork muscle as a function of frequency. A force is imposed on the lower surface of the sample and acceleration is measured on its upper surface. These two parameters are measured using sensors. The sample is modeled by Kelvin-Voigt model. These measures allow deducing the change in the mechanical impedance modulus (/Zexp/ = /Force: Acceleration/) of pork muscle as a function of vibration frequency. The measured impedance has a resonance of approximately 60Hz. Best-fit parameters of theoretical impedance can be deduced by superposition with the experiment result. The variation of Young’s modulus and internal damping of pig’s muscle as a function of frequency are determined. The results obtained between 5Hz and 30Hz are the same as determined by Aimedieu and al in 2003, therefore validating our technique. The Young’s modulus of muscle increases with the frequency, on the other hand, we note a rating decrease of internal damping.

  20. Long-Term Internal Variability Effects on Centennial Dynamic Sea Level Projections

    Science.gov (United States)

    Hadi Bordbar, Mohammad; Martin, Thomas; Park, Wonsun; Latif, Mojib

    2015-04-01

    The Earth's surface is warming in response to anthropogenic emissions of greenhouse gases, especially carbon dioxide (CO2). Sea level rise is one of the most pressing aspects of global warming with far-reaching consequences for coastal societies. However, sea level rise did and will strongly vary from coast to coast. Here we investigate the long-term internal variability effects on centennial projections of dynamic sea level (DSL), the local departure from the globally averaged sea level. A large ensemble of global warming integrations was conducted with a climate model, where each ensemble member was forced by identical CO2-increase but started from different atmospheric and oceanic initial conditions taken from an unforced millennial control run. In large parts of the mid- and high latitudes, the ensemble spread of the projected centennial DSL trends is of the same order of magnitude as the globally averaged steric sea level rise, suggesting internal variability cannot be ignored when assessing 21st century DSL changes. This conclusion is also supported by analyzing projections with other climate models. The ensemble spread is strongly reduced in the mid- to high latitudes if only the atmospheric initial conditions are perturbed; suggesting uncertainty in the projected centennial DSL trends there is largely due to the lack of ocean information. Thus climate model projections of regional sea level would benefit from ocean initialization.

  1. Internal dynamics and membership of the NGC 3603 Young Cluster from microarcsecond astrometry

    CERN Document Server

    Rochau, Boyke; Stolte, Andrea; Gennaro, Mario; Gouliermis, Dimitrios; Da Rio, Nicola; Dzyurkevich, Natalia; Henning, Thomas; 10.1088/2041-8205/716/1/L90

    2010-01-01

    We have analyzed two epochs of HST/WFPC2 observations of the young Galactic starburst cluster in NGC 3603 with the aim to study its internal dynamics and stellar population. Relative proper motions measured over 10.15 yrs of more than 800 stars enable us to distinguish cluster members from field stars. The best-fitting isochrone yields Av=4.6-4.7 mag, a distance of 6.6-6.9 kpc, and an age of 1 Myr for NGC 3603 Young Cluster (NYC). We identify pre-main-sequence/main-sequence transition stars located in the short-lived radiative-convective gap, which in the NYC occurs in the mass range 3.5-3.8 Msun. We also identify a sparse population of stars with an age of 4 Myr, which appear to be the lower mass counterparts to previously discovered blue supergiants located in the giant HII region NGC 3603. For the first time, we are able to measure the internal velocity dispersion of a starburst cluster from 234 stars with I < 18.5 mag to {\\sigma}_pm1D=141+/-27 {\\mu}as/yr (4.5+/-0.8 km/s at a distance of 6.75 kpc). As s...

  2. 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.

  3. Steered molecular dynamics study of inhibitor binding in the internal binding site in dehaloperoxidase-hemoglobin.

    Science.gov (United States)

    Zhang, Zhisen; Santos, Andrew P; Zhou, Qing; Liang, Lijun; Wang, Qi; Wu, Tao; Franzen, Stefan

    2016-04-01

    The binding free energy of 4-bromophenol (4-BP), an inhibitor that binds in the internal binding site in dehaloperoxidase-hemoglobin (DHP) was calculated using Molecular Dynamics (MD) methods combined with pulling or umbrella sampling. The effects of systematic changes in the pulling speed, pulling force constant and restraint force constant on the calculated potential of mean force (PMF) are presented in this study. The PMFs calculated using steered molecular dynamics (SMD) were validated by umbrella sampling (US) in the strongly restrained regime. A series of restraint force constants ranging from 1000 down to 5 kJ/(mol nm(2)) were used in SMD simulations. This range was validated using US, however noting that weaker restraints give rise to a broader sampling of configurations. This comparison was further tested by a pulling simulation conducted without any restraints, which was observed to have a value closest to the experimentally measured free energy for binding of 4-BP to DHP based on ultraviolet-visible (UV-vis) and resonance Raman spectroscopies. The protein-inhibitor system is well suited for fundamental study of free energy calculations because the DHP protein is relatively small and the inhibitor is quite rigid. Simulation configuration structures are compared to the X-ray crystallography structures of the binding site of 4-BP in the distal pocket above the heme.

  4. Dynamic Analysis of Coolant Channel and Its Internals of Indian 540 MWe PHWR Reactor

    Directory of Open Access Journals (Sweden)

    N. Dharmaraju

    2008-01-01

    Full Text Available The horizontal coolant channel is one of the important parts of primary heat transport system in PHWR type of reactors. There are in all 392 channels in the core of Indian 540 MWe reactor. Each channel houses 13 natural uranium fuel bundles and shielding and sealing plugs one each on either side of the channel. The heavy water coolant flows through the coolant channel and carries the nuclear heat to outside the core for steam generation and power production in the turbo-generator. India has commissioned one 540 MWe PHWR reactor in September 2005 and another similar unit will be going into operation very shortly. For a complete dynamic study of the channel and its internals under the influence of high coolant flow, experimental and modeling studies have been carried out. A good correlation has been achieved between the results of experimental and analytical models. The operating life of a typical coolant channel typically ranges from 10 to 15 full-power years. Towards the end of its operating life, its health monitoring becomes an important activity. Vibration diagnosis plays an important role as a tool for life management of coolant. Through the study of dynamic characteristics of the coolant channel under simulated loading condition, an attempt has been made to develop a diagnostics to monitor the health of the coolant channel over its operating life. A study has been also carried out to characterize the fuel vibration under different flow condition.

  5. 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...

  6. 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.

  7. 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.

  8. Intramolecular Vibrational Energy Redistribution (ivr) in Selected S_{1} Levels above 1000 cm^{-1} in Para-Fluorotoluene

    Science.gov (United States)

    Whalley, Laura E.; Gardner, Adrian M.; Tuttle, William Duncan; Davies, Julia A.; Reid, Katharine L.; Wright, Timothy G.

    2017-06-01

    With increasing vibrational wavenumber, the density of states of a molecule is expected to rise dramatically, especially so when low wavenumber torsions (internal rotations) are present, as in the case of para-fluorotoluene (pFT). This in turn is expected to lead to more opportunities for coupling between vibrational modes, which is the driving force for intramolecular vibrational energy redistribution (IVR). Previous studies at higher energies have focussed on the two close lying vibrational levels at 1200 cm^{-1} in the S_{1} electronic state of pFT which were assigned to two zero-order bright states (ZOBSs), whose characters predominantly involve C-CH_{3} and C-F stretching modes. A surprising result of these studies was that the photoelectron spectra showed evidence that IVR is more extensive following excitation of the C-F mode than it is following excitation of the C-CH_{3} mode, despite these levels being separated by only 35 cm^{-1}. This observation provides evidence that the IVR dynamics are mode-specific, which in turn may be a consequence of the IVR route being dependent on couplings to nearby states that are only available to the C-F mode. In this work, in order to further investigate this behaviour, we have employed resonance-enhanced multiphoton ionisation (REMPI) spectroscopy and zero-kinetic-energy (ZEKE) spectroscopy to probe S_{1} levels above 1000 cm^{-1} in pFT. Such ZEKE spectra have been recorded via a number of S_{1} intermediate levels allowing the character and coupling between vibrations to be unravelled; the consequence of this coupling will be discussed with a view to understanding any IVR dynamics seen. C. J. Hammond, V. L. Ayles, D. E. Bergeron, K. L. Reid and T. G. Wright, J. Chem. Phys., 125, 124308 (2006) J. A. Davies, A. M. Green, A. M. Gardner, C. D. Withers, T. G. Wright and K. L. Reid, Phys. Chem. Chem. Phys., 16, 430 (2014)

  9. Linking external and internal salt geometries - a key to understanding salt dynamics

    Science.gov (United States)

    Kukla, Peter; Urai, Janos

    2014-05-01

    Considering the growing importance of salt in the energy, food and waste disposal industries, this paper reviews the status quo and major developments in salt research over the last decade. As a way forward in order to close identified gaps in knowledge, an integrated salt basin evaluation concept is proposed appreciating both external and internal geometries and properties. Examples of key studies in the Central European Basin and the South Oman Salt basin show that such a model may improve our understanding of the multi-scale processes operating in salt terrains. The workflow proposed allows to better asses (i) the initiation and maintenance of salt dynamics, (ii) the evolution of the internal structure of evaporites during halokinesis in salt giants, (iii) the coupling of processes in the evaporites and the salt's under- and overburden. It will lead to a better integration of the different data sets and resulting models, which will provide new insights into the structural evolution of salt giants. Finally it will also stimulate new concepts for (i) the initiation dynamics of halokinesis, (ii) the rheology and mechanics of the evaporites by brittle and ductile processes, (iii) the coupling of processes in the evaporites and the under- and overburden, and (iv) the impact of the layered evaporite rheology on the structural evolution. As an outlook for future research to be initiated in salt terrains we still need to improve our database on evaporite rocks especially the ones which take changes of properties in time into account. This includes for example the dependencies of thermal and mechanical properties on changes in strain, pressure and temperature or external and internal geometry changes relating to slow geological processes. Also geomechanical modelling efforts can be significantly improved by making full use of the data available on the effects of water, and some of the discrepancies seen in experimental data on different salts can probably be explained in

  10. Intramolecular versus intermolecular hydrogen bonding in solution

    NARCIS (Netherlands)

    Vliegenthart, J.F.G.; Kroon, Jan; Kroon-Batenburg, L.M.J.; Leeflang, B.R.

    1994-01-01

    The balance between intra- and intermolecular hydrogen bonding is studied for a solution of methyl beta-cellobioside in water and dimethylsulfoxide by 1H NMR and molecular dynamics simulations. In water O(3) predominantly interacts with water molecules, whereas in dimethylsulfoxide it is

  11. Molecular dynamics model of dimethyl ether

    Energy Technology Data Exchange (ETDEWEB)

    Lin, B.; Halley, W.J. [Univ. of Minnesota, Minneapolis, MN (United States)

    1995-11-02

    We report a molecular dynamics model of the monomeric liquid dimethyl ether. The united atom approach is used to treat CH{sub 3} groups as point source centers. Partial charges are derived from the experimental dipole moment. Harmonic force constants are used for intramolecular interactions, and their values are so chosen that the model`s fundamental frequencies agree with experimental results. Because we are interested in solvation properties, the model contains flexible molecules, allowing molecular distortion and internal dynamical quantities. We report radial distribution functions and the static structure factors as well as some dynamical quantities such as the dynamical structure factor, infrared absorption, and Raman scattering spectra. Calculated results agree reasonably well with experimental and other simulation results. 25 refs., 8 figs., 1 tab.

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

    DEFF Research Database (Denmark)

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

    2014-01-01

    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, and the ...

  13. Intramolecular Amide Hydrolysis in N-Methylmaleamic Acid Revisited

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    The intramolecular amide hydrolysis of N-methylmaleamic acid have been revisited by use of density functional theory and inclusion of solvent effects. The results indicate that concerted reaction mechanism is favored over stepwise reaction mechanism. This is in agreement with the previous theoretical study. Sovlent effects have significant influence on the reaction barrier.

  14. 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...

  15. 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 of compou

  16. Exploration of Salt Wedge Dynamics in the Columbia River Estuary Using Optical Measurements of Internal Ship Wakes.

    Science.gov (United States)

    Holman, R. A.; Greydanus, S. J.

    2014-12-01

    In May of 2013 and beyond, Argus optical measurements of the mouth of the Columbia River estuary and plume were collected as part of the RIVET II multi-investigator field experiment. One surprise was the strength of eddy and internal wave signatures observed in movies computed from one-minute averages of high-frequency snapshots (such that gravity waves were averaged out but slicks and variable surface roughness remained). In particular, passing ships left wakes that propagated away at speeds on the order of 0.5 m/s, much slower than gravity waves and presumably surface manifestations of internal waves associated with the time-varying salt-wedge. Thus, these internal ship wakes appear to act as probes of internal stratification dynamics. This paper will explore the time variations of these internal wakes and relate them to corresponding variations in the estuary salt wedge.

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

    OpenAIRE

    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 as states for the conservation laws of the dynamic model. Temperature, pressure, and the amount and composition of the phases are calculated on the basis of these states at every time step. The Red...

  18. Blue Straggler Stars in Globular Clusters: a powerful tool to probe the internal dynamical evolution of stellar systems

    CERN Document Server

    Ferraro, Francesco R; Dalessandro, Emanuele; Mucciarelli, Alessio; Lovisi, Loredana

    2014-01-01

    This chapter presents an overview of the main observational results obtained to date about Blue Straggler Stars (BSSs) in Galactic Globular Clusters (GCs). The BSS specific frequency, radial distribution, chemical composition and rotational properties are presented and discussed in the framework of using this stellar population as probe of GC internal dynamics. In particular, the shape of the BSS radial distribution has been found to be a powerful tracer of the dynamical age of stellar systems, thus allowing the definition of the first empirical "dynamical clock".

  19. Modified virtual internal bond model for concrete subjected to dynamic loading

    Science.gov (United States)

    Patil, Mayuri

    Concrete is often used as a primary material to build protective structures. There is a wide range of research work being performed to simulate the behavior of reinforced concrete under impact and blast loading. This behavior is studied from both material and structural points of view. The research study presented in this thesis focuses on material aspects of modeling. LS-DYNARTM is an effective software for modeling and finite element analysis of structural members. It allows the user to define the material through commercially available or user-defined constitutive material models. Each material model has a distinct set of parameters to define a material which is further assigned to elements and used for simulations. This research study presents a user defined material model called Modified Concrete Virtual Internal Bond Model (MC-VIB). The basic constitutive model of VIB assumes the body as a collection of randomly oriented material points interconnected by a network of internal bonds. The model was modified by several researchers for different purposes. This research presents the MC-VIB for concrete under dynamic loading and studies its implementation into LS-DYNARTM. The modifications include incorporation of shear behavior and accounting for the difference in behavior of concrete in tension and compression. This project includes the calibration of the model based on stress-strain behavior of single element and cylinder model of concrete. The parameters are based on concrete with a uniaxial compressive strength of 27.6 MPa (4 ksi). These numerical curves are compared to those obtained from conventionally used material models for concrete and standard curves obtained by accepted equations to check the accuracy of prediction. The material model available in LS-DYNARTM requires a number of input parameters to define concrete behavior. These properties are normally derived from actual tests performed on the concrete under consideration. Often the properties are

  20. The influence of a model subglacial lake on ice dynamics and internal layering

    Directory of Open Access Journals (Sweden)

    E. Gudlaugsson

    2015-07-01

    Full Text Available As ice flows over a subglacial lake, the drop in bed resistance leads to an increase in ice velocities and a subsequent draw-down of isochrones and cold ice from the surface. The ice surface flattens as it adjusts to the lack of resisting forces at the base. The rapid transition in velocity induces changes in temperature and ice viscosity, releasing deformation energy which raises the temperature locally. Recent studies of Antarctic subglacial lakes indicate that many lakes experience very fast and possibly episodic drainage, during which the lake size is rapidly reduced as water flows out. A question is what effect this would have on internal layers within the ice, and whether such past events could be inferred from isochrone structures downstream. Here, we study the effect of a subglacial lake on the dynamics of a model ice stream as well as the influence that such short timescale drainage would have on the internal layers of the ice. To this end, we use a Full–Stokes, polythermal ice flow model. An enthalpy gradient method is used to account for the evolution of temperature and water content within the ice. We find that the rapid transition between slow-moving ice outside the lake, and full sliding over the lake, releases large amounts of deformational energy, which has the potential to form a temperate layer at depth in the transition zone. In addition, we provide an explanation for a characteristic surface feature, commonly seen at the edges of subglacial lakes, a hummocky surface depression in the transition zone between little to full sliding. We also conclude that rapid changes in lake geometry or basal friction create a travelling wave at depth within the isochrone structure that transfers downstream with the advection of ice, thus indicating the possibility of detecting past events with ice penetrating radar.

  1. 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.

  2. Empirical Evidence for Impacts of Internal Migration on Vegetation Dynamics in China from 1982 to 2000.

    Science.gov (United States)

    Song, Conghe; Lord, Jackson W; Zhou, Liming; Xiao, Jingfeng

    2008-08-27

    Migration is one of the major socio-economic characteristics of China since the country adopted the policy of economic reform in late 1970s. Many studies have been dedicated to understand why and how people move, and the consequences of their welfare. The purpose of this study is to investigate the environmental impacts of the large scale movement of population in China. We analyzed the trend in the Normalized Difference Vegetation Index (NDVI) from the Advanced Very High Resolution Radiometer (AVHRR) along with China migration data from the 1 percent national survey during 1982-1987, the 4(th) national census during 1985-1990 and the 5(th) national census during1995~2000. We found that the internal migration in China has a statistically significant negative impact on vegetation growth at the provincial scale from 1982 to 2000 even though the overall vegetation abundance increased in China. The impact from migration (R²=0.47, P=0.0001) on vegetation dynamics is the second strongest as among the factors considered, including changes in annual mean air temperature (R²=0.50, P=0.0001) and annual total precipitation (R²=0.30, P=0.0049) and gross domestic production (R²= 0.25, P=0.0102). The negative statistical relationship between the rate of increase in total migration and the change in vegetation abundance is stronger (R²=0.56, P=0.0000) after controlling for the effects of changes in temperature and precipitation. In-migration dominates the impacts of migration on vegetation dynamics. Therefore, it is important for policy makers in China to take the impacts of migration on vegetation growth into account while making policies aiming at sustainable humanenvironment relations.

  3. 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…

  4. FOREWORD: Third International Symposium on Instability and Bifurcations in Fluid Dynamics

    Science.gov (United States)

    Bar-Yoseph, P. Z.; Brøns, M.; Cliffe, K. A.; Gelfgat, A.; Oron, A.

    2010-01-01

    Hydrodynamic stability is of fundamental importance in fluid dynamics and is a well-established subject of scientific investigation that continues to attract great interest of the fluid mechanics community. Bifurcations and instabilities are observed in all areas of fundamental and applied fluid dynamics and remain a challenge for experimental, theoretical and computational studies. Hydrodynamic instabilities of prototypical character are, for example, the Rayleigh-Bénard, the Taylor-Couette, the Bénard-Marangoni, the Rayleigh-Taylor, and the Kelvin-Helmholtz instabilities. A fundamental understanding of various patterns of bifurcations such as identifying the most dominant mechanisms responsible for the instability threshold is also required if one is to design reliable and efficient industrial processes and applications, such as melting, mixing, crystal growth, coating, welding, flow re-attachment over wings, and others. Modeling of various instability mechanisms in biological and biomedical systems is currently a very active and rapidly developing area of research with important biotechnological and medical applications (biofilm engineering, wound healing, etc). The understanding of breaking symmetry in hemodynamics could have important consequences for vascular biology and diseases and its implication for vascular interventions (grafting, stenting, etc). The collection of papers in this volume is a selection of the presentations given at the Third International Symposium on Instability and Bifurcations in Fluid Dynamics, University of Nottingham, UK, 10-13 August 2009. With more than 100 invited and contributed papers the symposium gave an overview of the state-of-the art of the field including experimental, theoretical, and computational approaches to problems related to convection, effects of magnetic fields, wake flows, rotating flows, and many others. The complete program can be found at the conference website. The symposium was the follow-up of two

  5. The dynamical environment of asteroid 21 Lutetia according to different internal models

    Science.gov (United States)

    Aljbaae, S.; Chanut, T. G. G.; Carruba, V.; Souchay, J.; Prado, A. F. B. A.; Amarante, A.

    2017-01-01

    One of the most accurate models currently used to represent the gravity field of irregular bodies is the polyhedral approach. In this model, the mass of the body is assumed to be homogeneous, which may not be true for a real object. The main goal of the this paper is to study the dynamical effects induced by three different internal structures (uniform, three- and four-layered) of asteroid (21) Lutetia, an object that recent results from space probe suggest being at least partially differentiated. The Mascon gravity approach used in the this work consists of dividing each tetrahedron into eight parts to calculate the gravitational field around the asteroid. The zero-velocity curves show that the greatest displacement of the equilibrium points occurs in the position of the E4 point for the four-layered structure and the smallest one occurs in the position of the E3 point for the three-layered structure. Moreover, stability against impact shows that the planar limit gets slightly closer to the body with the four-layered structure. We then investigated the stability of orbital motion in the equatorial plane of (21) Lutetia and propose numerical stability criteria to map the region of stable motions. Layered structures could stabilize orbits that were unstable in the homogeneous model.

  6. Internal Dynamics and Chiral Analysis of Pulegone, Using Microwave Broadband Spectroscopy

    Science.gov (United States)

    Krin, Anna; Perez, Cristobal; Schnell, Melanie; Quesada-Moreno, María del Mar; López-González, Juan Jesús; Avilés-Moreno, Juan Ramón; Pinacho, Pablo; Blanco, Susana; Lopez, Juan Carlos

    2017-06-01

    Essential oils, such as peppermint or pennyroyal oil, are widely used in medicine, pharmacology and cosmetics. Their major constituents, terpenes, are mostly chiral molecules and thus may exhibit different biological functionality with respect to their enantiomers. Here, we present recent results on the enantiomers of pulegone, one of the components of the peppermint (Mentha piperita L.) and pennyroyal (Mentha pulegium) essential oils, using the microwave three-wave mixing (M3WM) technique. M3WM relies on the fact that the scalar triple product of the dipole moment components μ_{a}, μ_{b} and μ_{c} differs in sign between the enantiomers. A loop of three dipole-allowed rotational transitions is required for the analysis of a chiral molecule. Since the recorded signal will be exactly out of phase for the two enantiomers, an unambiguous differentiation between them is possible, even in complex mixtures. In addition to the chiral analysis of pulegone, its internal dynamics, resulting from the independent rotation of two of its three methyl groups, will be discussed. Moreover, a cluster of pulegone with one water molecule will be presented.

  7. The dynamical environment of asteroid 21 Lutetia according to different internal models

    CERN Document Server

    Aljbaae, Safwan; Carruba, Valerio; Souchay, Jean; Prado, Antonio F B A; Amarante, André

    2016-01-01

    One of the most accurate models currently used to represent the gravity field of irregular bodies is the polyhedral approach. In this model, the mass of the body is assumed to be homogeneous, which may not be true for a real object. The main goal of the present paper is to study the dynamical effects induced by three different internal structures (uniform, three- and four-layers) of asteroid (21) Lutetia, an object that recent results from space probe suggest being at least partially differentiated. The Mascon gravity approach used in the present work, consists of dividing each tetrahedron into eight parts to calculate the gravitational field around the asteroid. The zero-velocity curves show that the greatest displacement of the equilibrium points occurs in the position of the E4 point for the four-layers structure and the smallest one occurs in the position of the E3 point for the three-layers structure. Moreover, stability against impact shows that the planar limit gets slightly closer to the body with the...

  8. PREFACE: International Conference on Control and Synchronization of Dynamical Systems (CSDS-2005)

    Science.gov (United States)

    Pisarchik, Alexander N.

    2005-01-01

    This volume of Journal of Physics: Conference Series contains selected articles by the participants at the International Conference on Control and Synchronization of Dynamical Systems (CSDS-2005) organized by Centro de Investigaciones en Optica (CIO) in cooperation with the Society for Industrial and Applied Mathematics (SIAM), which was held in Leon, Guanajuato, Mexico on 4-7 October 2005. CSDS-2005 featured the latest research in nonlinear dynamics concentrating on the theory of control and synchronization of complex systems and its applications in different areas of science and engineering, including optics, electronics, mechanics, chemistry, medicine, economy, communication, etc. The conference brought together leading researchers, both theoreticians and experimentalists, from different fields of science and provided an excellent opportunity for sharing ideas and problems among specialists in controlling dynamical systems and synchronization. The meeting served a dual purpose: to expose the scientific community to the cutting edge of forefront research done by leaders in this area from as many as 25 countries and to attract the attention of Mexican researchers to this field of science. These proceedings are intended to be a record of this conference and to serve as a reference for future research which the conference hopes to have initiated. After the pioneering work on controlling chaos of E Ott, C Grebogi and J Yorke appeared in Physical Review Letters in 1990, the number of works on this topic grew tremendously. Our extensive bibliographic search among 110 peer reviewed journals yielded more than 1500 papers on controlling chaos and more than 2500 on synchronization of chaotic systems published during the last decade. The numbers of publications are still at their peaks that began to saturate, in 1998 and 2003, respectively. It is my pleasure to acknowledge the contribution of the program and organizing committees, the funding agencies and cooperating

  9. 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.

  10. 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

    Energy Technology Data Exchange (ETDEWEB)

    Kroonblawd, Matthew P.; Sewell, Thomas D., E-mail: sewellt@missouri.edu [Department of Chemistry, University of Missouri-Columbia, Columbia, Missouri 65211-7600 (United States); Maillet, Jean-Bernard, E-mail: jean-bernard.maillet@cea.fr [CEA, DAM, DIF, F-91297 Arpajon (France)

    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.

  11. Cohesin, condensin, and the intramolecular centromere loop together generate the mitotic chromatin spring.

    Science.gov (United States)

    Stephens, Andrew D; Haase, Julian; Vicci, Leandra; Taylor, Russell M; Bloom, Kerry

    2011-06-27

    Sister chromatid cohesion provides the mechanistic basis, together with spindle microtubules, for generating tension between bioriented chromosomes in metaphase. Pericentric chromatin forms an intramolecular loop that protrudes bidirectionally from the sister chromatid axis. The centromere lies on the surface of the chromosome at the apex of each loop. The cohesin and condensin structural maintenance of chromosomes (SMC) protein complexes are concentrated within the pericentric chromatin, but whether they contribute to tension-generating mechanisms is not known. To understand how pericentric chromatin is packaged and resists tension, we map the position of cohesin (SMC3), condensin (SMC4), and pericentric LacO arrays within the spindle. Condensin lies proximal to the spindle axis and is responsible for axial compaction of pericentric chromatin. Cohesin is radially displaced from the spindle axis and confines pericentric chromatin. Pericentric cohesin and condensin contribute to spindle length regulation and dynamics in metaphase. Together with the intramolecular centromere loop, these SMC complexes constitute a molecular spring that balances spindle microtubule force in metaphase.

  12. The role of hydrogen bonding in excited state intramolecular charge transfer.

    Science.gov (United States)

    Chipem, Francis A S; Mishra, Anasuya; Krishnamoorthy, G

    2012-07-07

    Intramolecular charge transfer (ICT) that occurs upon photoexcitation of molecules is a vital process in nature and it has ample applications in chemistry and biology. The ICT process of the excited molecules is affected by several environmental factors including polarity, viscosity and hydrogen bonding. The effect of polarity and viscosity on the ICT processes is well understood. But, despite the fact that hydrogen bonding significantly influences the ICT process, the specific role of hydrogen bonding in the formation and stabilization of the ICT state is not unambiguously established. Some literature reports predicted that the hydrogen bonding of the solvent with a donor promotes the formation of a twisted intramolecular charge transfer (TICT) state. Some other reports stated that it inhibits the formation of the TICT state. Alternatively, it was proposed that the hydrogen bonding of the solvent with an acceptor favors the TICT state. It is also observed that a dynamic equilibrium is established between the free and the hydrogen bonded ICT states. This perspective focuses on the specific role played by hydrogen bonding of the solvent with the donor and the acceptor, and by proton transfer in the ICT process. The utility of such influence in molecular recognition and anion sensing is discussed with a few recent literature examples in the end.

  13. Recent insights into intramolecular 13C isotope composition of biomolecules

    Science.gov (United States)

    Gilbert, A.; Yamada, K.; Julien, M.; Yoshida, N.; Remaud, G.; Robins, R.

    2016-12-01

    In 1961 Abelson & Hoering shown that the intramolecular 13C distribution in amino acids was not homogeneous, namely the carboxylic acid positions were 13C-enriched compared with the mean of the remaining C-atoms in the molecule [1]. Nearly 20 years later, Monson & Hayes were able to demonstrate that even and odd positions in acetogenic fatty acids also showed non-statistical 13C isotope distributions, and that the pattern varied depending on the organism [2]. It took a further decade for the intramolecular 13C distribution in the key metabolite, glucose, to be defined [3]. Although informative, much of this work was incomplete, a number of positions having to be deduced by difference. This limitation arose mainly due to the lack of techniques enabling the separation and quantification of 13C isotopomers of the target molecule. In the past decade, quantitative 13C NMR has been developed for the determination of the intramolecular isotope composition of a given molecule with a precision of 1‰ or better [4]. This breakthrough has made possible a comprehensive view of the determinants governing intramolecular isotope composition of biological molecules. In particular, it can be shown that intramolecular pattern in sugars is influenced by the C-assimilation pathway and by post-photosynthetic fractionation associated with carbohydrate metabolism [5]. In addition, analysis by NMR of the alkyl chain of acetogenic lipids (fatty acids, n-alkanes) shows an alternation between odd and even C-atom positions, as observed by Monson& Hayes [2], throughout the molecule [6]. Overall, it is becoming apparent that this pattern is influenced by two principal metabolic factors: (i) the 13C pattern extant in the starting compounds; (ii) isotope fractionation associated with the enzymes involved in the biosynthetic pathway. On the whole, the determination of intramolecular isotope patterns in biomolecules allows better insights into the conditions and pathways by which they are formed

  14. Sensitivity of emergent sociohydrologic dynamics to internal system properties and external sociopolitical factors: Implications for water management

    Science.gov (United States)

    Elshafei, Y.; Tonts, M.; Sivapalan, M.; Hipsey, M. R.

    2016-06-01

    It is increasingly acknowledged that effective management of water resources requires a holistic understanding of the coevolving dynamics inherent in the coupled human-hydrology system. One of the fundamental information gaps concerns the sensitivity of coupled system feedbacks to various endogenous system properties and exogenous societal contexts. This paper takes a previously calibrated sociohydrology model and applies an idealized implementation, in order to: (i) explore the sensitivity of emergent dynamics resulting from bidirectional feedbacks to assumptions regarding (a) internal system properties that control the internal dynamics of the coupled system and (b) the external sociopolitical context; and (ii) interpret the results within the context of water resource management decision making. The analysis investigates feedback behavior in three ways, (a) via a global sensitivity analysis on key parameters and assessment of relevant model outputs, (b) through a comparative analysis based on hypothetical placement of the catchment along various points on the international sociopolitical gradient, and (c) by assessing the effects of various direct management intervention scenarios. Results indicate the presence of optimum windows that might offer the greatest positive impact per unit of management effort. Results further advocate management tools that encourage an adaptive learning, community-based approach with respect to water management, which are found to enhance centralized policy measures. This paper demonstrates that it is possible to use a place-based sociohydrology model to make abstractions as to the dynamics of bidirectional feedback behavior, and provide insights as to the efficacy of water management tools under different circumstances.

  15. Nonlinear Dynamic Analysis of Coupled Gear-Rotor-Bearing System with the Effect of Internal and External Excitations

    Institute of Scientific and Technical Information of China (English)

    ZHOU Shihua; SONG Guiqiu; REN Zhaohui; WEN Bangchun

    2016-01-01

    Extensive studies on nonlinear dynamics of gear systems with internal excitation or external excitation respectively have been carried out. However, the nonlinear characteristics of gear systems under combined internal and external excitations are scarcely investigated. An eight-degree-of-freedom(8-DOF) nonlinear spur gear-rotor-bearing model, which contains backlash, transmission error, eccentricity, gravity and input/output torque, is established, and the coupled lateral-torsional vibration characteristics are studied. Based on the equations of motion, the coupled spur gear-rotor-bearing system(SGRBS) is investigated using the Runge-Kutta numerical method, and the effects of rotational speed, error fluctuation and load fluctuation on the dynamic responses are explored. The results show that a diverse range of nonlinear dynamic characteristics such as periodic motion, quasi-periodic motion, chaotic behaviors and impacts exhibited in the system are strongly attributed to the interaction between internal and external excitations. Significantly, the changing rotational speed could effectively control the vibration of the system. Vibration level increases with the increasing error fluctuation. Whereas the load fluctuation has an influence on the nonlinear dynamic characteristics and the increasing excitation force amplitude makes the vibration amplitude increase, the chaotic motion may be restricted. The proposed model and numerical results can be used for diagnosis of faults and vibration control of practical SGRBS.

  16. Nonlinear dynamic analysis of coupled gear-rotor-bearing system with the effect of internal and external excitations

    Science.gov (United States)

    Zhou, Shihua; Song, Guiqiu; Ren, Zhaohui; Wen, Bangchun

    2016-03-01

    Extensive studies on nonlinear dynamics of gear systems with internal excitation or external excitation respectively have been carried out. However, the nonlinear characteristics of gear systems under combined internal and external excitations are scarcely investigated. An eight-degree-of-freedom(8-DOF) nonlinear spur gear-rotor-bearing model, which contains backlash, transmission error, eccentricity, gravity and input/output torque, is established, and the coupled lateral-torsional vibration characteristics are studied. Based on the equations of motion, the coupled spur gear-rotor-bearing system(SGRBS) is investigated using the Runge-Kutta numerical method, and the effects of rotational speed, error fluctuation and load fluctuation on the dynamic responses are explored. The results show that a diverse range of nonlinear dynamic characteristics such as periodic motion, quasi-periodic motion, chaotic behaviors and impacts exhibited in the system are strongly attributed to the interaction between internal and external excitations. Significantly, the changing rotational speed could effectively control the vibration of the system. Vibration level increases with the increasing error fluctuation. Whereas the load fluctuation has an influence on the nonlinear dynamic characteristics and the increasing excitation force amplitude makes the vibration amplitude increase, the chaotic motion may be restricted. The proposed model and numerical results can be used for diagnosis of faults and vibration control of practical SGRBS.

  17. Intramolecular Aminocyanation of Alkenes via N–CN Bond Cleavage**

    Science.gov (United States)

    Pan, Zhongda; Pound, Sarah M.; Rondla, Naveen R.; Douglas, Christopher J.

    2014-01-01

    A metal-free, Lewis acid-promoted intramolecular aminocyanation of alkenes was developed. B(C6F5)3 activates N-sulfonyl cyanamides, leading an formal cleavage of the N-CN bonds in conjunction with vicinal addition of sulfonamide and nitrile groups across an alkene. This method enables atom-economical access to indolines and tetrahydroquinolines in excellent yields, and provides a complementary strategy for regioselective alkene difunctionalizations with sulfonamide and nitrile groups. Labeling experiments with 13C suggest a fully intramolecular cyclization pattern due to lack of label scrambling in double crossover experiments. Catalysis with Lewis acid is realized and the reaction can be conducted under air. PMID:24719371

  18. Intramolecular aminocyanation of alkenes by N-CN bond cleavage.

    Science.gov (United States)

    Pan, Zhongda; Pound, Sarah M; Rondla, Naveen R; Douglas, Christopher J

    2014-05-12

    A metal-free, Lewis acid promoted intramolecular aminocyanation of alkenes was developed. B(C6F5)3 activates N-sulfonyl cyanamides, thus leading to a formal cleavage of the N-CN bonds in conjunction with vicinal addition of sulfonamide and nitrile groups across an alkene. This method enables atom-economical access to indolines and tetrahydroquinolines in excellent yields, and provides a complementary strategy for regioselective alkene difunctionalizations with sulfonamide and nitrile groups. Labeling experiments with (13)C suggest a fully intramolecular cyclization pattern due to the lack of label scrambling in double crossover experiments. Catalysis with Lewis acid is realized and the reaction can be conducted under air. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. 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.

  20. Intramolecular amide bonds stabilize pili on the surface of bacilli

    Energy Technology Data Exchange (ETDEWEB)

    Budzik, Jonathan M.; Poor, Catherine B.; Faull, Kym F.; Whitelegge, Julian P.; He, Chuan; Schneewind, Olaf; (UC); (UCLA-MED)

    2010-01-12

    Gram-positive bacteria elaborate pili and do so without the participation of folding chaperones or disulfide bond catalysts. Sortases, enzymes that cut pilin precursors, form covalent bonds that link pilin subunits and assemble pili on the bacterial surface. We determined the x-ray structure of BcpA, the major pilin subunit of Bacillus cereus. The BcpA precursor encompasses 2 Ig folds (CNA{sub 2} and CNA{sub 3}) and one jelly-roll domain (XNA) each of which synthesizes a single intramolecular amide bond. A fourth amide bond, derived from the Ig fold of CNA{sub 1}, is formed only after pilin subunits have been incorporated into pili. We report that the domains of pilin precursors have evolved to synthesize a discrete sequence of intramolecular amide bonds, thereby conferring structural stability and protease resistance to pili.

  1. Experimental and computational study on photophysical properties of substituted o-hydroxy acetophenone derivatives: Intramolecular proton transfer and solvent effect

    Energy Technology Data Exchange (ETDEWEB)

    Mitra, S. [Department of Chemistry, North-Eastern Hill University, Permanent Campus, Umshing, Shillong 793 022 (India)], E-mail: smitra@nehu.ac.in; Singh, T. Sanjoy [Department of Chemistry, North-Eastern Hill University, Permanent Campus, Umshing, Shillong 793 022 (India); Mandal, A.; Mukherjee, S. [Department of Physical Chemistry, Indian Association for the Cultivation of Science, Jadavpur, Calcutta 700 032 (India)

    2007-12-06

    The intramolecular proton transfer reaction, relative stability of different conformers arising from the internal torsional motion and effect of solvent on the photophysical properties in the ground (S{sub 0}) as well as first excited singlet (S{sub 1}) state is studied for two prototype intramolecularly hydrogen bonded o-hydroxy acetophenone analogues, namely 2-acetyl-4-methyl-6-nitrophenol (I) and 2-acetyl-4-chloro-6-nitrophenol (II) by steady state and time-resolved fluorescence spectroscopy and density functional theory. In addition to the enol (E) structure suitable for excited state intramolecular proton transfer (pro-ESIPT), two non-ESIPT enol conformers (E1 and E2) are also predicted in the ground state. Exothermic ESIPT from E results largely Stokes shifted tautomeric emission for both the compounds. On the other hand, the excited state photophysics of E1 or E2 is largely controlled by the nature of the solvent. TDDFT calculation with B3LYP/6-31++G(d,p) method reproduces the experimental results in these systems much better than hybrid functionals like BHandHLYP, MPWPW91 and MPWB1K.

  2. Experimental and computational study on photophysical properties of substituted o-hydroxy acetophenone derivatives: Intramolecular proton transfer and solvent effect

    Science.gov (United States)

    Mitra, S.; Singh, T. Sanjoy; Mandal, A.; Mukherjee, S.

    2007-12-01

    The intramolecular proton transfer reaction, relative stability of different conformers arising from the internal torsional motion and effect of solvent on the photophysical properties in the ground (S 0) as well as first excited singlet (S 1) state is studied for two prototype intramolecularly hydrogen bonded o-hydroxy acetophenone analogues, namely 2-acetyl-4-methyl-6-nitrophenol ( I) and 2-acetyl-4-chloro-6-nitrophenol ( II) by steady state and time-resolved fluorescence spectroscopy and density functional theory. In addition to the enol ( E) structure suitable for excited state intramolecular proton transfer ( pro-ESIPT), two non-ESIPT enol conformers ( E1 and E2) are also predicted in the ground state. Exothermic ESIPT from E results largely Stokes shifted tautomeric emission for both the compounds. On the other hand, the excited state photophysics of E1 or E2 is largely controlled by the nature of the solvent. TDDFT calculation with B3LYP/6-31++G(d,p) method reproduces the experimental results in these systems much better than hybrid functionals like BHandHLYP, MPWPW91 and MPWB1K.

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

    Science.gov (United States)

    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.

  4. The Physical Chemistry of the Intramolecular Cyclodehydration Reactions of Prepolymers

    Science.gov (United States)

    Rabinovich, I. B.; Karyakin, Nikolai V.; Rusanov, Aleksandr L.; Korshak, V. V.

    1986-07-01

    The experimental data on the thermodynamics of the intramolecular cyclodehydration reactions of prepolymers in the solid phase are examined and treated systematically. The changes in the thermodynamic functions of the above processes have been analysed in detail over a wide temperature range. The temperature ranges corresponding to the formation of polyheteroarylenes which are "defect-free" to the maximum extent have been estimated. The bibliography includes 65 references.

  5. Ultrafast excited-state intramolecular proton transfer of aloesaponarin I.

    Science.gov (United States)

    Nagaoka, Shin-ichi; Uno, Hidemitsu; Huppert, Dan

    2013-04-25

    Time-resolved emission of aloesaponarin I was studied with the fluorescence up-conversion and time-correlated single-photon-counting techniques. The rates of the excited-state intramolecular proton transfer, of the solvent and molecular rearrangements, and of the decay from the excited proton-transferred species were determined and interpreted in the light of time-dependent density functional calculations. These results were discussed in conjunction with UV protection and singlet-oxygen quenching activity of aloe.

  6. Synthesis of Normorphans through an Efficient Intramolecular Carbamoylation of Ketones.

    Science.gov (United States)

    Diaba, Faïza; Montiel, Juan A; Serban, Georgeta; Bonjoch, Josep

    2015-08-01

    An unexpected C-C bond cleavage was observed in trichloroacetamide-tethered ketones under amine treatment and exploited to develop a new synthesis of normophans from 4-amidocyclohexanones. The reaction involves an unprecedented intramolecular haloform-type reaction of trichloroacetamides promoted by enamines (generated in situ from ketones) as counter-reagents. The methodology was applied to the synthesis of compounds embodying the 6-azabicyclo[3.2.1]octane framework.

  7. Strong light fields coax intramolecular reactions on femtosecond time scales

    CERN Document Server

    Krishnamurthy, M; Mathur, D

    2004-01-01

    Energetic H$_2^+$ ions are formed as a result of intra-molecular rearrangement during fragmentation of linear alcohols (methanol, ethanol, propanol, hexanol, and dodecanol) induced by intense optical fields produced by 100 fs long, infrared, laser pulses of peak intensity 8$\\times10^{15}$ W cm$^{-2}$. Polarization dependent measurements show, counterintuitively, that rearrangement is induced by the strong optical field within a single laser pulse, and that it occurs before Coulomb explosion of the field-ionized multiply charged alcohols.

  8. 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.

  9. 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.

  10. Mechanism of intramolecular photostabilization in self-healing cyanine fluorophores.

    Science.gov (United States)

    van der Velde, Jasper H M; Ploetz, Evelyn; Hiermaier, Matthias; Oelerich, Jens; de Vries, Jan Willem; Roelfes, Gerard; Cordes, Thorben

    2013-12-16

    Organic fluorophores, which are popular labels for microscopy applications, intrinsically suffer from transient and irreversible excursions to dark-states. An alternative to adding photostabilizers at high concentrations to the imaging buffer relies on the direct linkage to the fluorophore. However, the working principles of this approach are not yet fully understood. In this contribution, we investigate the mechanism of intramolecular photostabilization in self-healing cyanines, in which photodamage is automatically repaired. Experimental evidence is provided to demonstrate that a single photostabilizer, that is, the vitamin E derivative Trolox, efficiently heals the cyanine fluorophore Cy5 in the absence of any photostabilizers in solution. A plausible mechanism is that Trolox interacts with the fluorophore through intramolecular quenching of triplet-related dark-states, which is a mechanism that appears to be common for both triplet-state quenchers (cyclooctatetraene) and redox-active compounds (Trolox, ascorbic acid, methylviologen). Additionally, the influence of solution-additives, such as cysteamine and procatechuic acid, on the self-healing process are studied. The results suggest the potential applicability of self-healing fluorophores in stochastic optical reconstruction microscopy (STORM) with optical super-resolution. The presented data contributes to an improved understanding of the mechanism involved in intramolecular photostabilization and has high relevance for the future development of self-healing fluorophores, including their applications in various research fields.

  11. 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.

  12. Intramolecular hydrogen migration in alkylperoxy and hydroperoxyalkylperoxy radicals: accurate treatment of hindered rotors.

    Science.gov (United States)

    Sharma, Sandeep; Raman, Sumathy; Green, William H

    2010-05-13

    We have calculated the thermochemistry and rate coefficients for stable molecules and reactions in the title reaction families using CBS-QB3 and B3LYP/CBSB7 methods. The accurate treatment of hindered rotors for molecules having multiple internal rotors with potentials that are not independent of each other can be problematic, and a simplified scheme is suggested to treat them. This is particularly important for hydroperoxyalkylperoxy radicals (HOOQOO). Two new thermochemical group values are suggested in this paper, and with these values, the group additivity method for calculation of enthalpy as implemented in reaction mechanism generator (RMG) gives good agreement with CBS-QB3 predictions. The barrier heights follow the Evans-Polanyi relationship for each type of intramolecular hydrogen migration reaction studied.

  13. 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...... molecules internally labelled with two fixed fluorophores, we demonstrate the accuracy and precision of our method using the known structure of double-stranded DNA as a benchmark, resolve 10-base-pair differences in fluorophore separations, and determine the unique 3D orientation of each DNA molecule...... and using only simple means, we simultaneously determine both the relative (x,y)-separation of the fluorophores and their individual orientations in space with accuracy and precision. The positions and orientations of two domains of the same molecule are thus time-resolved. Using short double-stranded DNA...

  14. 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

  15. The Thermal Conductivity of Carbon Nanotubes with Defects and Intramolecular Junctions

    Directory of Open Access Journals (Sweden)

    Qiaoli Zhou

    2013-01-01

    Full Text Available The thermal conductivity of various carbon nanotubes with defects or intramolecular junctions was studied using nonequilibrium molecular dynamics approach. The results show that the thermal conductivity of both armchair and zigzag carbon nanotubes increased with the decrease of the radius of the tube. The thermal conductivity of armchair tube is higher than that of zigzag tube when the radii of the two tubes are kept almost same. Discontinuities appear on the temperature profile along the tube axial at the region of IMJ, resulting in the large temperature gradient and thus lower thermal conductivity of (n,n/(m,0 tube with one IMJ and (m,0/(n,n/(m,0 tube with two IMJs. For the (m,0/(n,n/(m,0 tube with two IMJs, phonon mean free path of the middle (n,n tube is much smaller than that of the isolate (n,n tube.

  16. Intramolecular triplet energy transfer in anthracene-based platinum acetylide oligomers.

    Science.gov (United States)

    Li, Yongjun; Köse, Muhammet E; Schanze, Kirk S

    2013-08-01

    Platinum acetylide oligomers that contain an anthracene moiety have been synthesized and subjected to photophysical characterization. Spectroscopic measurement and DFT calculations reveal that both the singlet and triplet energy levels of the anthracene segment are lower than those of the platinum acetylide segment. Thus, the platinum acetylide segment acts as a sensitizer to populate the triplet state of the anthrancene segment via intramolecular triplet-triplet energy transfer. The objective of this work is to understand the mechanisms of energy-transfer dynamics in these systems. Fluorescence quenching and the dominant triplet absorption that arises from the anthracene segment in the transient absorption spectrum of Pt4An give clear evidence that energy transfer adopts an indirect mechanism, which begins with singlet-triplet energy transfer from the anthracene segment to the platinum acetylide segment followed by triplet-triplet energy transfer to the anthracene segment.

  17. Synthesis and Characterization of Tetrahydrofurfurylcyclopentadienyl Molybdenum Tricarbonyl Dimer: Evidence for 19-Electron Intramolecular "Solvento" Interactions.

    Science.gov (United States)

    Gallagher, Michelle; Dougherty, Pat; Tanner, Pamela S.; Barbini, Denis C.; Schulte, Jurgen; Jones, Wayne E.

    1999-06-14

    The synthesis and characterization of a THF pendant, dimeric Mo cyclopentadienyl complex is reported and the structure characterized by NMR, FTIR, and UV-vis spectroscopies. The dimer was found to undergo metal-metal bond homolysis under either photochemical or electrochemical conditions to yield an odd-electron complex. Cyclic voltammetry under varying scan rate conditions from 25 to 10 000 mV/s demonstrates a dynamic equilibrium process that we assign to the formation of either an intramolecular 19-electron (18 + delta) complex or a bare 17-electron complex. Photolysis of the dimer in room temperature solution could be monitored as a loss of the dpi-dsigma transition at 503 nm by transient absorption spectroscopy. The recovery of the transient absorption signal at 410 nm follows first-order kinetics at a rate of 5 x 10(3) s(-1).

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. 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…

  3. 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

  4. 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

  5. An investigation of the internal temperature dependence of Pd-Pt cluster beam deposition: A molecular dynamics study

    Science.gov (United States)

    Chen, Cha'o.-Kuang; Chang, Shing-Cheng

    2010-02-01

    We investigated the internal temperature dependence of the Pd 1- aPt a cluster beam deposition in the present study via the molecular dynamics simulations of soft-landing. By analysis of the velocity distribution and diffusion coefficient of the bimetallic cluster, Pd atoms with better mobility improved the diffusibility of Pt atoms. The radial composition distribution showed that a Pt-core/Pd-shell structure of the cluster formed at high internal temperatures through migrations of the Pd atoms from inner to surface shells. In the soft-landing process, the diffusing and epitaxial behaviors of the deposited clusters mainly depended on the internal temperature because the incident energy of the cluster was very small. By depositing clusters at high internal temperatures, we obtained a thin film of good epitaxial growth as the energetic cluster impact. Furthermore, nonepitaxial configurations such as scattered nonepitaxial atoms, misoriented particles, and grain boundaries of (1 1 1) planes were produced in the growth of the cluster-assembled film. As the size of the incident cluster increased, the internal temperature of the cluster needed for better interfacial diffusion and contact epitaxy on the substrate also rose.

  6. A discrete chemo-dynamical model of the dwarf spheroidal galaxy Sculptor: mass profile, velocity anisotropy and internal rotation

    Science.gov (United States)

    Zhu, Ling; van de Ven, Glenn; Watkins, Laura L.; Posti, Lorenzo

    2016-11-01

    We present a new discrete chemo-dynamical axisymmetric modelling technique, which we apply to the dwarf spheroidal galaxy Sculptor. The major improvement over previous Jeans models is that realistic chemical distributions are included directly in the dynamical modelling of the discrete data. This avoids loss of information due to spatial binning and eliminates the need for hard cuts to remove contaminants and to separate stars based on their chemical properties. Using a combined likelihood in position, metallicity and kinematics, we find that our models naturally separate Sculptor stars into a metal-rich and a metal-poor population. Allowing for non-spherical symmetry, our approach provides a central slope of the dark matter density of γ = 0.5 ± 0.3. The metal-rich population is nearly isotropic (with β _r^{red} = 0.0± 0.1), while the metal-poor population is tangentially anisotropic (with β _r^{blue} = -0.2± 0.1) around the half-light radius of 0.26 kpc. A weak internal rotation of the metal-rich population is revealed with vmax/σ0 = 0.15 ± 0.15. We run tests using mock data to show that a discrete data set with ˜6000 stars is required to distinguish between a core (γ = 0) and cusp (γ = 1), and to constrain the possible internal rotation to better than 1σ confidence with our model. We conclude that our discrete chemo-dynamical modelling technique provides a flexible and powerful tool to robustly constrain the internal dynamics of multiple populations, and the total mass distribution in a stellar system.

  7. 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...

  8. Human ceruloplasmin. Intramolecular electron transfer kinetics and equilibration

    DEFF Research Database (Denmark)

    Farver, O; Bendahl, L; Skov, L K

    1999-01-01

    Pulse radiolytic reduction of disulfide bridges in ceruloplasmin yielding RSSR(-) radicals induces a cascade of intramolecular electron transfer (ET) processes. Based on the three-dimensional structure of ceruloplasmin identification of individual kinetically active disulfide groups and type 1 (T1...... and indeed electron equilibration between T1A and the trinuclear copper center in the domain 1-6 interface takes place with a rate constant of 2.9 +/- 0.6 s(-1). The equilibrium constant is 0.17. Following reduction of T1A Cu(II), another ET process takes place between RSSR(-) and T1B copper(II) of domain 4...

  9. High-pressure effects on intramolecular electron transfer compounds

    CERN Document Server

    He Li Ming; Li Hong; Zhang Bao Wen; Li Yi; Yang Guo Qiang

    2002-01-01

    We explore the effect of pressure on the fluorescence spectra of the intramolecular electron transfer compound N-(1-pyrenylmethyl), N-methyl-4-methoxyaniline (Py-Am) and its model version, with poly(methyl methacrylate) blended in, at high pressure up to 7 GPa. The emission properties of Py-Am and pyrene show distinct difference with the increase of pressure. This difference indicates the strength of the charge transfer interaction resulting from the adjusting of the conformation of Py-Am with increase of pressure. The relationship between the electronic state of the molecule and pressure is discussed.

  10. 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.

  11. Acculturative stress and influential factors among international students in China: a structural dynamic perspective.

    Science.gov (United States)

    Yu, Bin; Chen, Xinguang; Li, Shiyue; Liu, Yang; Jacques-Tiura, Angela J; Yan, Hong

    2014-01-01

    Stress represents a prominent aspect of modern life and is associated with numerous negative health consequences. International students are a key force in shaping globalization. However, these students often experience acculturative stress, influencing their health and well-being. The growing number of international students in China emerges as a new global health challenge and presents an opportunity to advance our understanding of acculturative stress. This study aims to investigate the acculturative stress of international students in China, and verify the mechanism and influential factors of acculturative stress. We analyzed survey data from 567 international students attending universities in Wuhan, China. We used a network-based analytical approach to assess the structure of the Acculturative Stress Scale for International Students and used regression analysis to assess the relationships between acculturative stress and theoretically related factors. We found that higher levels of acculturative stress were reported by students from Asia and Africa than from other regions (Europe/America/Oceania). Lower acculturative stress was reported by unmarried students than others and by students well prepared than not well prepared. We verified seven acculturative stress subconstructs: rejection, identity threat, opportunity deprivation, self-confidence, value conflict, cultural competence, and homesickness; and discovered a three-dimensional network structure of these subconstructs. Our results suggest that acculturative stress was more common among international students in China than in developed countries. Acculturative stress was also more common among international students who did not well prepared, married, and belonged to an organized religion. African and Asian students' stress was higher than that for students from other regions. Acculturative stress prevention programs should seek to improve preparedness of the international students for studying abroad and

  12. Acculturative stress and influential factors among international students in China: a structural dynamic perspective.

    Directory of Open Access Journals (Sweden)

    Bin Yu

    Full Text Available Stress represents a prominent aspect of modern life and is associated with numerous negative health consequences. International students are a key force in shaping globalization. However, these students often experience acculturative stress, influencing their health and well-being. The growing number of international students in China emerges as a new global health challenge and presents an opportunity to advance our understanding of acculturative stress. This study aims to investigate the acculturative stress of international students in China, and verify the mechanism and influential factors of acculturative stress. We analyzed survey data from 567 international students attending universities in Wuhan, China. We used a network-based analytical approach to assess the structure of the Acculturative Stress Scale for International Students and used regression analysis to assess the relationships between acculturative stress and theoretically related factors. We found that higher levels of acculturative stress were reported by students from Asia and Africa than from other regions (Europe/America/Oceania. Lower acculturative stress was reported by unmarried students than others and by students well prepared than not well prepared. We verified seven acculturative stress subconstructs: rejection, identity threat, opportunity deprivation, self-confidence, value conflict, cultural competence, and homesickness; and discovered a three-dimensional network structure of these subconstructs. Our results suggest that acculturative stress was more common among international students in China than in developed countries. Acculturative stress was also more common among international students who did not well prepared, married, and belonged to an organized religion. African and Asian students' stress was higher than that for students from other regions. Acculturative stress prevention programs should seek to improve preparedness of the international students for

  13. METHODS OF CHAOTIC DYNAMICS IN SCHEMES OF RESEARCHES FEASIBILITY INTERNALS OF CAR TRAFFIC VOLUMES

    National Research Council Canada - National Science Library

    H. A. Kramarenko; A. V. Nechay; V. V. Skalozub

    2011-01-01

    The possibilities of chaotic dynamics methods applied to the topical analysis and forecasting problems of economic and technological properties of wagon streams represented by the related time series are studied...

  14. Measuring the rate of intramolecular contact formation in polypeptides

    Science.gov (United States)

    Lapidus, Lisa; Eaton, William; Hofrichter, James

    2001-03-01

    Formation of a specific contact between two residues of a polypeptide chain is an important elementary process in protein folding. Here we describe a method for studying contact formation between tryptophan and cysteine based on measurements of the lifetime of the tryptophan triplet state. With tryptophan at one end of a flexible peptide and cysteine at the other, the triplet decay rate is identical to the rate of quenching by cysteine and is also close to the diffusion-limited rate of contact formation. The length dependence of this end-to-end contact rate was studied in a series of Cys-(Ala-Gly-Gln)_k-Trp peptides, with k varying from 1 to 6. The rate decreases from -1/(40 ns) for k = 1 to -1/(140 ns) for k = 6, approaching the length-dependence expected for a random coil (n-3/2) for the longest peptides. Comparing the intramolecular and bimolecular quenching rates for cysteine with two disulfide molecules (cystine and lipoate) determines the ratio of the equilibrium constants for forming the intramolecular and bimolecular contact pairs. This ratio depends on the persistence length of the chain and is therefore a measure of the flexibility of the polypeptide.

  15. Intramolecular hydrogen-bonding studies by NMR spectroscopy

    CERN Document Server

    Cantalapiedra, N A

    2000-01-01

    o-methoxybenzamide and N-methyl-o-methylbenzamide, using the pseudo-contact shifts calculated from the sup 1 H and sup 1 sup 3 C NMR spectra. The main conformation present in solution for o-fluorobenzamide was the one held by an intramolecular N-H...F hydrogen bond. Ab-initio calculations (at the RHF/6-31G* level) have provided additional data for the geometry of the individual molecules. A conformational equilibrium study of some nipecotic acid derivatives (3-substituted piperidines: CO sub 2 H, CO sub 2 Et, CONH sub 2 , CONHMe, CONEt sub 2) and cis-1,3-disubstituted cyclohexane derivatives (NHCOMe/CO sub 2 Me, NHCOMe/CONHMe, NH sub 2 /CO sub 2 H) has been undertaken in a variety of solvents, in order to predict the intramolecular hydrogen-bonding energies involved in the systems. The conformer populations were obtained by direct integration of proton peaks corresponding to the equatorial and axial conformations at low temperature (-80 deg), and by geometrically dependent coupling constants ( sup 3 J sub H s...

  16. Intramolecular carbon isotope distribution of acetic acid in vinegar.

    Science.gov (United States)

    Hattori, Ryota; Yamada, Keita; Kikuchi, Makiko; Hirano, Satoshi; Yoshida, Naohiro

    2011-09-14

    Compound-specific carbon isotope analysis of acetic acid is useful for origin discrimination and quality control of vinegar. Intramolecular carbon isotope distributions, which are each carbon isotope ratios of the methyl and carboxyl carbons in the acetic acid molecule, may be required to obtain more detailed information to discriminate such origin. In this study, improved gas chromatography-pyrolysis-gas chromatography-combustion-isotope ratio mass spectrometry (GC-Py-GC-C-IRMS) combined with headspace solid-phase microextraction (HS-SPME) was used to measure the intramolecular carbon isotope distributions of acetic acid in 14 Japanese vinegars. The results demonstrated that the methyl carbons of acetic acid molecules in vinegars produced from plants were mostly isotopically depleted in (13)C relative to the carboxyl carbon. Moreover, isotopic differences (δ(13)C(carboxyl) - δ(13)C(methyl)) had a wide range from -0.3 to 18.2‰, and these values differed among botanical origins, C3, C4, and CAM plants.

  17. Heuristic RNA pseudoknot prediction including intramolecular kissing hairpins

    Science.gov (United States)

    Sperschneider, Jana; Datta, Amitava; Wise, Michael J.

    2011-01-01

    Pseudoknots are an essential feature of RNA tertiary structures. Simple H-type pseudoknots have been studied extensively in terms of biological functions, computational prediction, and energy models. Intramolecular kissing hairpins are a more complex and biologically important type of pseudoknot in which two hairpin loops form base pairs. They are hard to predict using free energy minimization due to high computational requirements. Heuristic methods that allow arbitrary pseudoknots strongly depend on the quality of energy parameters, which are not yet available for complex pseudoknots. We present an extension of the heuristic pseudoknot prediction algorithm DotKnot, which covers H-type pseudoknots and intramolecular kissing hairpins. Our framework allows for easy integration of advanced H-type pseudoknot energy models. For a test set of RNA sequences containing kissing hairpins and other types of pseudoknot structures, DotKnot outperforms competing methods from the literature. DotKnot is available as a web server under http://dotknot.csse.uwa.edu.au. PMID:21098139

  18. Intramolecular bond length dependence of the anisotropic dispersion coefficients for interactions of rare gas atoms with N2, CO, Cl2, HCl and HBr

    Science.gov (United States)

    Hettema, Hinne; Wormer, Paul E. S.; Thakkar, Ajit J.

    Ab initio many body perturbation theory is used to calculate the imaginary frequency multipole polarizabilities of N2, Cl2, CO, HCl and HBr as a function of bond length. These are combined with previously calculated dynamic polarizabilities for rare gas atoms to obtain the intramolecular bond length dependence of the anisotropic dispersion and induction coefficients through R-8 for AB-X (AB = N2, Cl2, CO, HCl, HBr and X = He, Ne, Ar, Kr, Xe) interactions.

  19. Excited state intramolecular charge transfer reaction of 4-(morpholenyl) benzonitrile in solution: Effects of hetero atom in the donor moiety

    Indian Academy of Sciences (India)

    Tuhin Pradhan; Harun Al Rasid Gazi; Ranjit Biswas

    2010-07-01

    An intramolecular charge transfer (ICT) molecule with an extra hetero atom in its donor moiety has been synthesized in order to investigate how ICT reaction is affected by hetero atom replacement. Photo-physical and photo-dynamical properties of this molecule, 4-(morpholenyl)benzonitrile (M6C), have been studied in 20 different solvents. The correlation between the reaction driving force (- ) and activation barrier ( #) has been explored in order to understand the solvent effects (static and dynamic) on the photo-excited ICT reaction in this molecule. A Kramer’s model analysis of the experimentally observed reaction rate constants indicates a solvent-averaged activation barrier of ∼ 4 in the absence of solvent dynamical control. The reaction in M6C is therefore not a barrier-less reaction but close to the limit where conventional kinetics might break down.

  20. 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)

  1. Analysis of internal resonance in a two-degree-of-freedom nonlinear dynamical system

    Science.gov (United States)

    Dai, Honghua; Wang, Xuechuan; Schnoor, Matt; Atluri, Satya N.

    2017-08-01

    This study is devoted to the analysis of the three-to-one internal resonance in a two degree-of-freedom system with cubic nonlinearity. Quasi-periodic motion is found to appear in the present system with internal resonance, while it does not show up in the case without internal resonance. Both the time domain collocation method and the harmonic balance method are applied to obtain the periodic solutions, and are compared with the benchmark solution of the numerical integration method. In contrast, the quasi-periodic solutions can only be captured via the numerical integration method. A combination of the phase plane portrait, Poincare map, and the frequency spectrum are employed to identify the quasi-periodic motions. A peculiar bifurcation-of-attraction-basin phenomenon is found and demonstrated. Moreover, for strongly nonlinear system subject to high external force, a long-lived chaotic transient is observed.

  2. Flat panel X-ray detector with reduced internal scattering for improved attenuation accuracy and dynamic range

    Energy Technology Data Exchange (ETDEWEB)

    Smith, Peter D. (Santa Fe, NM); Claytor, Thomas N. (White Rock, NM); Berry, Phillip C. (Albuquerque, NM); Hills, Charles R. (Los Alamos, NM)

    2010-10-12

    An x-ray detector is disclosed that has had all unnecessary material removed from the x-ray beam path, and all of the remaining material in the beam path made as light and as low in atomic number as possible. The resulting detector is essentially transparent to x-rays and, thus, has greatly reduced internal scatter. The result of this is that x-ray attenuation data measured for the object under examination are much more accurate and have an increased dynamic range. The benefits of this improvement are that beam hardening corrections can be made accurately, that computed tomography reconstructions can be used for quantitative determination of material properties including density and atomic number, and that lower exposures may be possible as a result of the increased dynamic range.

  3. 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...... 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......, this supports the view of “repressed” migration flows for that period....

  4. Generalized Dynamics of the Mass Point with Internal Degrees of Freedom

    CERN Document Server

    Tarakanov, A N

    2010-01-01

    An equation of motion of the mass point with internal degrees of freedom in scalar potential $U$ depending on relative coordinates and time, velocity and accelerations is obtained both for non-relativistic and relativistic case. In non-relativistic case a generalization of the energy conservation law follows, if $\\partial U / \\partial t = 0$ fulfilled. A concept of work is generalized to relativistic case, leading to corresponding integral of motion, if $\\partial U / \\partial \\tau = 0$ fulfilled, where $\\tau$ is proper time of the point. In neglecting an internal degrees of freedom and absence of interaction this integral of motion gives standard Special Relativity.

  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...... quantitative method for analyzing internallayercontinuity—named the continuity-index. When applied to data from Pine Island Glacier, West Antarctica, the new method clearly identifies a continuum of discontinuity of internallayers that corresponds with the current ice-velocity field. The analysis provides...

  6. 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;).

  7. 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

  8. 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 mana

  9. 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 mana

  10. A Dynamic Analysis of Social Capital-Building of International and UK Students

    Science.gov (United States)

    Rienties, Bart; Johan, Novie; Jindal-Snape, Divya

    2015-01-01

    Although many international students experience transitional issues, most research assumes these issues will disappear over time. Using principles of social capital theory, this study addressed whether after three years of study students were able to build multi-national and host social capital links. In this quantitative study of 81 students from…

  11. A Dynamic Analysis of Social Capital-Building of International and UK Students

    Science.gov (United States)

    Rienties, Bart; Johan, Novie; Jindal-Snape, Divya

    2015-01-01

    Although many international students experience transitional issues, most research assumes these issues will disappear over time. Using principles of social capital theory, this study addressed whether after three years of study students were able to build multi-national and host social capital links. In this quantitative study of 81 students from…

  12. Mixing, Internal Waves and Mesoscale Dynamics in the East China Sea

    Science.gov (United States)

    2007-09-30

    Journal of Marine Systems . I. Lozovatsky presented the results at the 39th International Liege Colloquium, “Ocean Turbulence, Re-revisited” in May...2007b. Liu, Z., H. Wei, I.D. Lozovatsky, and H.J.S. Fernando, Late summer stratification and turbulence in the Yellow Sea., Journal of Marine Systems , 2007

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

    Science.gov (United States)

    Wang, Daifeng; He, Fei; Maslov, Sergei; Gerstein, Mark

    2016-10-01

    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 evolutionarily

  14. 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

  15. Structure and internal rotation dynamics of the acetone-neon complex studied by microwave spectroscopy

    Science.gov (United States)

    Gao, Jiao; Seifert, Nathan A.; Thomas, Javix; Xu, Yunjie; Jäger, Wolfgang

    2016-12-01

    The microwave spectra of the van der Waals complexes acetone-20Ne and acetone-22Ne were measured using a cavity-based supersonic jet Fourier-transform microwave spectrometer in the region from 5 to 18 GHz. For these two isotopologues, both c- and weaker a-type transitions were observed. The transitions are split into multiplets due to the internal rotation of the two methyl groups in acetone. Initial electronic structure calculations were performed at the MP2/6-311++g (2d, p) level of theory and the internal rotation barrier height of the methyl groups was calculated to be ∼2.8 kJ/mol. The ab initio rotational constants were the basis for the spectroscopic searches, but the multiplet structures and floppiness of the complex made the quantum number assignment very difficult. The assignment was finally achieved with the aid of constructing closed frequency loops and predicting internal rotation splittings using the XIAM internal rotation program. The acetone methyl group tunneling barrier height was determined experimentally to be 3.10(6) kJ mol-1 [259(5) cm-1] in the acetone-Ne complex, which is lower than in the acetone monomer but comparable to the acetone-Ar complex (Kang et al., 2002). Experimental data and high-level CCSD(T)/aug-cc-pVTZ calculations suggest that the Ne atom lies directly above the plane formed by the carbonyl group and the two carbon-carbon bonds, which is different than the slightly offset position found previously in the acetone-Ar complex. Additionally, ab initio calculations and Quantum Theory of Atoms in Molecules analyses were used to analyze the methyl internal rotation motions in acetone and acetone-Ne.

  16. 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.

  17. Aspects of secondary bonding intramolecular interaction in organomercury and organochalcogen derivatives

    Indian Academy of Sciences (India)

    Sagar Sharma; Tapash Chakraborty; Kriti Srivastava; Harkesh B Singh

    2011-03-01

    Recent trends in the area of intramolecularly coordinated organomercury and organochalcogens derivatives are reviewed. Intramolecular coordination in organomercury derivatives facilitates the formation of mercurametallamacrocycle and leads to novel metal-metal interaction with closed shell ions. It also plays a key role in stabilizing telluroxanes as well as in the activation of chalcogen-carbon bonds.

  18. Mechanism of intramolecular charge transfer in DNA helix as probed by the use of the fluorescent 2-aminopurine

    Institute of Scientific and Technical Information of China (English)

    ZHANG Huijuan; WANG Peng; WANG Xuefei; FENG Juan; XU Sichuan; AI Xicheng; ZHANG Xingkang; ZHANG Jianping

    2004-01-01

    As a structural analogue of adenine, 2-aminopurine (2Ap) is often used as a fluorescent probe to study the intramolecular charge transfer reaction in DNA. We have designed and synthesized a series of model DNA helix with the variation in the distance between the 2Ap probe and the GGG sequence, and have investigated, by means of picosecond time-resolved fluorescence spectroscopy, the effect of the length of the bridge (consisting of a number of transfer dynamics. The fluorescence dynamics of 2Ap exhibited three exponential decay components, the one with a time constant of a few hundred picoseconds is assigned to the intramolecular charge transfer from GGG to 2Ap. Within 2.4 nm of the donor-acceptor separation,the rate of charge transfer decreased exponentially upon increasing the separation, from which the decay factor ,β is determined to be 1.3 nm-1. Beyond 2.4 nm, however, the rate started to increase, this abnormal behavior of charge transfer is interpreted in terms of the match of electronic energies between the I-bridge and the donor/acceptor couple.

  19. METHODS OF CHAOTIC DYNAMICS IN SCHEMES OF RESEARCHES FEASIBILITY INTERNALS OF CAR TRAFFIC VOLUMES

    Directory of Open Access Journals (Sweden)

    H. A. Kramarenko

    2011-04-01

    Full Text Available The possibilities of chaotic dynamics methods applied to the topical analysis and forecasting problems of economic and technological properties of wagon streams represented by the related time series are studied. The advisability of using the generalized logistic map method for the construction of time series behavior operational forecasting is also determined.

  20. Dynamic Conditional Correlations in International Stock, Bond and Foreign Exchange Markets: Emerging Markets Evidence

    NARCIS (Netherlands)

    M.S. Hakim (Mohamad); M.J. McAleer (Michael)

    2009-01-01

    textabstractThe paper models the dynamic conditional correlations in emerging stock, bond and foreign exchange markets using the DCC model of Engle (2002) and the GARCC model of McAleer et al. (2008). The highly restrictive DCC model suggests that the conditional correlations of the overall returns

  1. 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.)

  2. Actual Problems in Celestial Mechanics and Dynamical Astronomy, International Conference Cluj/Napoca, Romania, May 25-27, 2006

    Science.gov (United States)

    Érdi, B.; Szenkovits, F.

    2007-05-01

    In 25--27 May 2006 an International Conference on Actual Problems in Celestial Mechanics and Dynamical Astronomy was organized at Cluj-Napoca. The Faculty of Mathematics and Computer Science of the Babeş-Bolyai University, the host of this conference, organized this scientific meeting in collaboration with the Loránd Eötvös University (Budapest, Hungary), Sapientia University (Miercuria Ciuc, Romania), Astronomical Institute of the Romanian Academy (Bucharest, Romania) and Institute for Space Science (Bucharest, Romania). The main topics covered by the meeting were: - Solar-System dynamics, stability, resonances, chaos; - Dynamics of populations in the Solar System: NEAs, MBAs, Centaurs, KBOs, TNOs: observations, orbits, theoretical models; - Galactic and extragalactic dynamics; - Problems, models, methods and techniques in contemporary celestial mechanics and dynamical astronomy. The conference was structured into seven sessions of oral presentations, a poster session and a round table discussion. Each of the seven main sessions began with an invited lecture. These lectures reviewed the following fields: the Sitnikov problem (R. Dvorak, Austria); the age of the asteroid families (Z. Knezevic, Serbia and Montenegro); stability of exoplanetary systems (B. Érdi, Hungary); Saari's conjecture (Diacu, Canada); integrability from direct and inverse standpoints (G. Bozis, Greece); stability of exact solutions in restricted many-body problems (E. Grebenicov, Russia); actual Romanian research in post-Newtonian dynamics (V. Mioc, Romania). Beside the invited lectures, the 21 oral presentations covered the most various domains of celestial mechanics and dynamical astronomy. Chaotic behaviour was a premier topic. It was approached and studied by analytical, geometrical and numerical methods in many astronomical problems: the restricted three-body problem (with examples in the Solar System), the Gylden's model and its generalizations, capture domain, resonances, etc

  3. '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 ...

  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. Dynamic Conditional Correlations in International Stock, Bond and Foreign Exchange Markets: Emerging Markets Evidence

    OpenAIRE

    2009-01-01

    textabstractThe paper models the dynamic conditional correlations in emerging stock, bond and foreign exchange markets using the DCC model of Engle (2002) and the GARCC model of McAleer et al. (2008). The highly restrictive DCC model suggests that the conditional correlations of the overall returns are constant. In contrast, the GARCC model finds that the conditional correlations between bond-bond markets and between stock-stock markets are relatively constant across developed-emerging market...

  6. Direct Preparation of Carbon Nanotube Intramolecular Junctions on Structured Substrates

    Science.gov (United States)

    An, Jianing; Zhan, Zhaoyao; Sun, Gengzhi; Mohan, Hari Krishna Salila Vijayalal; Zhou, Jinyuan; Kim, Young-Jin; Zheng, Lianxi

    2016-12-01

    Leveraging the unique properties of single-walled carbon nanotube (SWNT) intramolecular junctions (IMJs) in innovative nanodevices and next-generation nanoelectronics requires controllable, repeatable, and large-scale preparation, together with rapid identification and comprehensive characterization of such structures. Here we demonstrate SWNT IMJs through directly growing ultralong SWNTs on trenched substrates. It is found that the trench configurations introduce axial strain in partially suspended nanotubes, and promote bending deformation in the vicinity of the trench edges. As a result, the lattice and electronic structure of the nanotubes can be locally modified, to form IMJs in the deformation regions. The trench patterns also enable pre-defining the formation locations of SWNT IMJs, facilitating the rapid identification. Elaborate Raman characterization has verified the formation of SWNT IMJs and identified their types. Rectifying behavior has been observed by electrical measurements on the as-prepared semiconducting-semiconducting (S-S) junction.

  7. Estimating the energy of intramolecular hydrogen bonds in chitosan oligomers

    Science.gov (United States)

    Mikhailov, G. P.; Lazarev, V. V.

    2016-07-01

    The effect the number of chitosan monomer units CTS n ( n = 1-5), the protonation of chitosan dimers, and the interaction between CTS n ( n = 1-3) and acetate ions have on the energy of intramolecular hydrogen bonds is investigated by means of QTAIM analysis and solving the vibrational problem within the cluster-continuum model. It is established that the number of H-bonds in CTS n is 2 n - 1 and the total energy of H-bonds grows by ~20 kJ/mol. It is concluded that the hydrogen bonds between CTS and acetate ions play a major role in the stabilization of polyelectrolyte complexes in dilute acetic acid solutions of CTS.

  8. Halo substituent effects on intramolecular cycloadditions involving furanyl amides.

    Science.gov (United States)

    Padwa, Albert; Crawford, Kenneth R; Straub, Christopher S; Pieniazek, Susan N; Houk, K N

    2006-07-21

    Intramolecular Diels-Alder reactions involving a series of N-alkenyl-substituted furanyl amides were investigated. Stable functionalized oxanorbornenes were formed in high yield upon heating at 80-110 degrees C. The cycloaddition reactions include several bromo-substituted furanyl amides, and these systems were found to proceed at a much faster rate and in higher yield than without substitution. This effect was observed by incorporating a halogen in the 3- or 5-position of the furan ring and appears to be general. The origin of increased cycloaddition rates for halo-substituted furans has been investigated with quantum mechanical calculations. The success of these reactions is attributed to increases in reaction exothermicities; this both decreases activation enthalpies and increases barriers to retrocycloadditions. Halogen substitution on furan increases reactant energy and stabilizes the product, which is attributed to the preference of electronegative halogens to be attached to a more highly alkylated and therefore more electropositive framework.

  9. INTERMOLECULAR AND INTRAMOLECULAR INTERACTIONS OF POLYMER GUAR GUM IN SOLUTIONS

    Institute of Scientific and Technical Information of China (English)

    Yun-fei Yan; Hai-yang Yang; Wen-yong Liu; Ping-ping Zhu; Ping-sheng He

    2005-01-01

    The tetrahedral borate ion can crosslink with polymer guar gum in aqueous solutions. If the concentration of guar gum is less than 0.045 g/dL, the intramolecular interaction between guar gum and borate ion increases due to the formation of crosslinks. As a result, the polymer chains of guar gum in solution shrink in size and the reduced viscosity of polymer solution decreases accordingly. On the other hand, if the concentration of guar gum is greater than 0.045 g/dL, the intermolecular interaction becomes apparent due to the same reason. The polymer chains, therefore, associate together and the reduced viscosity of polymer solution increases considerably. According to this technique, the critical concentration c*,presented by de-Gennes[1], is determined successfully.

  10. Stable morphology, but dynamic internal reorganisation, of interphase human chromosomes in living cells.

    Directory of Open Access Journals (Sweden)

    Iris Müller

    Full Text Available Despite the distinctive structure of mitotic chromosomes, it has not been possible to visualise individual chromosomes in living interphase cells, where chromosomes spend over 90% of their time. Studies of interphase chromosome structure and dynamics use fluorescence in-situ hybridisation (FISH on fixed cells, which potentially damages structure and loses dynamic information. We have developed a new methodology, involving photoactivation of labelled histone H3 at mitosis, to visualise individual and specific human chromosomes in living interphase cells. Our data revealed bulk chromosome volume and morphology are established rapidly after mitosis, changing only incrementally after the first hour of G1. This contrasted with the behaviour of specific loci on labelled chromosomes, which showed more progressive reorganisation, and revealed that "looping out" of chromatin from chromosome territories is a dynamic state. We measured considerable heterogeneity in chromosome decondensation, even between sister chromatids, which may reflect local structural impediments to decondensation and could potentially amplify transcriptional noise. Chromosome structure showed tremendous resistance to inhibitors of transcription, histone deacetylation and chromatin remodelling. Together, these data indicate steric constraints determine structure, rather than innate chromosome architecture or function-driven anchoring, with interphase chromatin organisation governed primarily by opposition between needs for decondensation and the space available for this to happen.

  11. Thin Films in Partial Wetting: Internal Selection of Contact-Line Dynamics

    Science.gov (United States)

    Alizadeh Pahlavan, Amir; Cueto-Felgueroso, Luis; McKinley, Gareth H.; Juanes, Ruben

    2015-07-01

    When a liquid touches a solid surface, it spreads to minimize the system's energy. The classic thin-film model describes the spreading as an interplay between gravity, capillarity, and viscous forces, but it cannot see an end to this process as it does not account for the nonhydrodynamic liquid-solid interactions. While these interactions are important only close to the contact line, where the liquid, solid, and gas meet, they have macroscopic implications: in the partial-wetting regime, a liquid puddle ultimately stops spreading. We show that by incorporating these intermolecular interactions, the free energy of the system at equilibrium can be cast in a Cahn-Hilliard framework with a height-dependent interfacial tension. Using this free energy, we derive a mesoscopic thin-film model that describes the statics and dynamics of liquid spreading in the partial-wetting regime. The height dependence of the interfacial tension introduces a localized apparent slip in the contact-line region and leads to compactly supported spreading states. In our model, the contact-line dynamics emerge naturally as part of the solution and are therefore nonlocally coupled to the bulk flow. Surprisingly, we find that even in the gravity-dominated regime, the dynamic contact angle follows the Cox-Voinov law.

  12. The Internal Dynamics of Fibrinogen and Its Implications for Coagulation and Adsorption.

    Directory of Open Access Journals (Sweden)

    Stephan Köhler

    2015-09-01

    Full Text Available Fibrinogen is a serum multi-chain protein which, when activated, aggregates to form fibrin, one of the main components of a blood clot. Fibrinolysis controls blood clot dissolution through the action of the enzyme plasmin, which cleaves fibrin at specific locations. Although the main biochemical factors involved in fibrin formation and lysis have been identified, a clear mechanistic picture of how these processes take place is not available yet. This picture would be instrumental, for example, for the design of improved thrombolytic or anti-haemorrhagic strategies, as well as, materials with improved biocompatibility. Here, we present extensive molecular dynamics simulations of fibrinogen which reveal large bending motions centered at a hinge point in the coiled-coil regions of the molecule. This feature, likely conserved across vertebrates according to our analysis, suggests an explanation for the mechanism of exposure to lysis of the plasmin cleavage sites on fibrinogen coiled-coil region. It also explains the conformational variability of fibrinogen observed during its adsorption on inorganic surfaces and it is supposed to play a major role in the determination of the hydrodynamic properties of fibrinogen. In addition the simulations suggest how the dynamics of the D region of fibrinogen may contribute to the allosteric regulation of the blood coagulation cascade through a dynamic coupling between the a- and b-holes, important for fibrin polymerization, and the integrin binding site P1.

  13. Thin Films in Partial Wetting: Internal Selection of Contact-Line Dynamics.

    Science.gov (United States)

    Alizadeh Pahlavan, Amir; Cueto-Felgueroso, Luis; McKinley, Gareth H; Juanes, Ruben

    2015-07-17

    When a liquid touches a solid surface, it spreads to minimize the system's energy. The classic thin-film model describes the spreading as an interplay between gravity, capillarity, and viscous forces, but it cannot see an end to this process as it does not account for the nonhydrodynamic liquid-solid interactions. While these interactions are important only close to the contact line, where the liquid, solid, and gas meet, they have macroscopic implications: in the partial-wetting regime, a liquid puddle ultimately stops spreading. We show that by incorporating these intermolecular interactions, the free energy of the system at equilibrium can be cast in a Cahn-Hilliard framework with a height-dependent interfacial tension. Using this free energy, we derive a mesoscopic thin-film model that describes the statics and dynamics of liquid spreading in the partial-wetting regime. The height dependence of the interfacial tension introduces a localized apparent slip in the contact-line region and leads to compactly supported spreading states. In our model, the contact-line dynamics emerge naturally as part of the solution and are therefore nonlocally coupled to the bulk flow. Surprisingly, we find that even in the gravity-dominated regime, the dynamic contact angle follows the Cox-Voinov law.

  14. 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.

  15. Statistical and dynamical analysis of internal waves on the continental shelf of the Middle Atlantic Bight from Space Shuttle photographs

    Science.gov (United States)

    Zheng, Quanan; Yan, Xiao-Hai; Klemas, Vic

    1993-01-01

    The internal waves on the continental shelf on the Middle Atlantic Bight seen on Space Shuttle photographs taken during the STS-40 mission in June 1991 are measured and analyzed. The internal wave field in the sample area has a three-level structure which consists of packet groups, packets, and solitons. An average packet group wavelength of 17.5 km and an average soliton wavelength of 0.6 km are measured. Finite-depth theory is used to derive the dynamic parameters of the internal solitons: the maximum amplitude of 5.6 m, the characteristic phase speed of 0.42 m/s, the characteristic period of 23.8 min, the velocity amplitude of the water particles in the upper and lower layers of 0.13 m/s and 0.030 m/s respectively, and the theoretical energy per unit crest line of 6.8 x 10 exp 4 J/m. The frequency distribution of solitons is triple-peaked rather than continuous. The major generation source is at 160 m water depth, and a second is at 1800 m depth, corresponding to the upper and lower edges of the shelf break.

  16. Deep evolutionary conservation of an intramolecular protein kinase activation mechanism.

    Directory of Open Access Journals (Sweden)

    Jingfen Han

    Full Text Available DYRK-family kinases employ an intramolecular mechanism to autophosphorylate a critical tyrosine residue in the activation loop. Once phosphorylated, DYRKs lose tyrosine kinase activity and function as serine/threonine kinases. DYRKs have been characterized in organisms from yeast to human; however, all entities belong to the Unikont supergroup, only one of five eukaryotic supergroups. To assess the evolutionary age and conservation of the DYRK intramolecular kinase-activation mechanism, we surveyed 21 genomes representing four of the five eukaryotic supergroups for the presence of DYRKs. We also analyzed the activation mechanism of the sole DYRK (class 2 DYRK present in Trypanosoma brucei (TbDYRK2, a member of the excavate supergroup and separated from Drosophila by ∼850 million years. Bioinformatics showed the DYRKs clustering into five known subfamilies, class 1, class 2, Yaks, HIPKs and Prp4s. Only class 2 DYRKs were present in all four supergroups. These diverse class 2 DYRKs also exhibited conservation of N-terminal NAPA regions located outside of the kinase domain, and were shown to have an essential role in activation loop autophosphorylation of Drosophila DmDYRK2. Class 2 TbDYRK2 required the activation loop tyrosine conserved in other DYRKs, the NAPA regions were critical for this autophosphorylation event, and the NAPA-regions of Trypanosoma and human DYRK2 complemented autophosphorylation by the kinase domain of DmDYRK2 in trans. Finally, sequential deletion analysis was used to further define the minimal region required for trans-complementation. Our analysis provides strong evidence that class 2 DYRKs were present in the primordial or root eukaryote, and suggest this subgroup may be the oldest, founding member of the DYRK family. The conservation of activation loop autophosphorylation demonstrates that kinase self-activation mechanisms are also primitive.

  17. 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...

  18. Computational fluid dynamics analysis on heat transfer and friction factor characteristics of a turbulent flow for internally grooved tubes

    Directory of Open Access Journals (Sweden)

    Selvaraj P.

    2013-01-01

    Full Text Available The article presents computational fluid dynamics studies on heat transfer, pressure drop, friction factor, Nusselt number and thermal hydraulic performance of a plain tube and tube equipped with the three types of internal grooves (circular, square and trapezoidal.Water was used as the working fluid. Tests were performed for Reynolds number ranges from 5000 to 13500 for plain tube and different geometry inside grooved tubes. The maximum increase of pressure drop was obtained from numerical modeling 74% for circular, 38% for square and 78% for trapezoidal grooved tubes were compared with plain tube. Based on computational fluid dynamics analysis the average Nusselt number was increased up to 37%, 26% and 42% for circular, square and trapezoidal grooved tubes respectively while compared with the plain tube. The thermal hydraulic performance was obtained from computational fluid dynamics analysis up to 38% for circular grooved tube, 27% for square grooved tube and 40% for trapezoidal grooved tube while compared with the plain tube.

  19. 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”.

  20. Modelling of the internal dynamics and density in a tens of joules plasma focus device

    Energy Technology Data Exchange (ETDEWEB)

    Marquez, Ariel [CNEA and Instituto Balseiro, 8402 Bariloche (Argentina); Gonzalez, Jose [INVAP-CONICET and Instituto Balseiro, 8402 Bariloche, Argentina. (Argentina); Tarifeno-Saldivia, Ariel; Pavez, Cristian; Soto, Leopoldo [CCHEN, Comision Chilena de Energia Nuclear, Casilla 188-D, Santiago (Chile); Center for Research and Applications in Plasma Physics and Pulsed Power, P4 (Chile); Clausse, Alejandro [CNEA-CONICET and Universidad Nacional del Centro, 7000 Tandil (Argentina)

    2012-01-15

    Using MHD theory, coupled differential equations were generated using a lumped parameter model to describe the internal behaviour of the pinch compression phase in plasma focus discharges. In order to provide these equations with appropriate initial conditions, the modelling of previous phases was included by describing the plasma sheath as planar shockwaves. The equations were solved numerically, and the results were contrasted against experimental measurements performed on the device PF-50J. The model is able to predict satisfactorily the timing and the radial electron density profile at the maximum compression.

  1. High-Speed Rotor Analytical Dynamics on Flexible Foundation Subjected to Internal and External Excitation

    Science.gov (United States)

    Jivkov, Venelin S.; Zahariev, Evtim V.

    2016-12-01

    The paper presents a geometrical approach to dynamics simulation of a rigid and flexible system, compiled of high speed rotating machine with eccentricity and considerable inertia and mass. The machine is mounted on a vertical flexible pillar with considerable height. The stiffness and damping of the column, as well as, of the rotor bearings and the shaft are taken into account. Non-stationary vibrations and transitional processes are analyzed. The major frequency and modal mode of the flexible column are used for analytical reduction of its mass, stiffness and damping properties. The rotor and the foundation are modelled as rigid bodies, while the flexibility of the bearings is estimated by experiments and the requirements of the manufacturer. The transition effects as a result of limited power are analyzed by asymptotic methods of averaging. Analytical expressions for the amplitudes and unstable vibrations throughout resonance are derived by quasi-static approach increasing and decreasing of the exciting frequency. Analytical functions give the possibility to analyze the influence of the design parameter of many structure applications as wind power generators, gas turbines, turbo-generators, and etc. A numerical procedure is applied to verify the effectiveness and precision of the simulation process. Nonlinear and transitional effects are analyzed and compared to the analytical results. External excitations, as wave propagation and earthquakes, are discussed. Finite elements in relative and absolute coordinates are applied to model the flexible column and the high speed rotating machine. Generalized Newton - Euler dynamics equations are used to derive the precise dynamics equations. Examples of simulation of the system vibrations and nonstationary behaviour are presented.

  2. Experimental Chiral Dynamics New Opportunities with Polarized Internal Targets and Almost-Real Photon Tagging

    CERN Document Server

    Bernstein, A M

    1998-01-01

    Experiments on pion (Goldstone Boson) photoproduction from the nucleon tests the ability to make QCD predictions at confinement scale energies. Experiments with both polarized beams and targets have the potential sensitivity to demonstrate the dynamic isospin breaking effects of the up and down quark mass difference, whereas experiments on Compton scattering from the nucleon will incisively probe its chiral structure by measuring all of the spin dependent amplitudes. These and other types of photo-induced measurements on nuclei could be possible at BLAST with the addition of an almost-real photon tagging system and a forward low energy recoil ion hodoscope.

  3. DYNAMICS MODEL AND SIMULATION OF FLAT VALVE SYSTEM OF INTERNAL COMBUSTION WATER PUMP

    Institute of Scientific and Technical Information of China (English)

    Zhang Hongxin; Zhang Tiezhu; Wang Yushun; Zhao Hong; Huo Wei

    2005-01-01

    The dynamics differential equations are constructed, and the initial conditions are also given. Simulation shows the following conclusions: The water pressure in cylinder has great instantaneous pulsation and phase step when outlet valve or inlet valve opens, but is more gently in other time; The volume efficiency is influenced by the output pressure slightly, and decreases as the working rotational speed increases; When the inherent frequency of the valves is integer multiple of the working frequency, the volume efficiency of system will decrease evidently.

  4. 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...

  5. Dynamics of Proton Transfer to Internal Water during the Photosynthetic Oxygen-Evolving Cycle.

    Science.gov (United States)

    Brahmachari, Udita; Barry, Bridgette A

    2016-11-10

    In photosynthesis, the light-driven oxidation of water is a sustainable process, which converts solar to chemical energy and produces protons and oxygen. To enable biomimetic strategies, the mechanism of photosynthetic oxygen evolution must be elucidated. Here, we provide information concerning a critical step in the oxygen-evolving, or S-state, cycle. During this S3-to-S0 transition, oxygen is produced, and substrate water binds to the manganese-calcium catalytic site. Our spectroscopic and H2(18)O labeling experiments show that this S3-to-S0 step is associated with the protonation of an internal water cluster in a hydrogen-bonding network, which contains calcium. When compared to the protonated water cluster, formed during a preceding step, the S1-to-S2 transition, the S3-to-S0 hydronium ion is likely to be coordinated by additional water molecules. This evidence shows that internal water and the hydrogen bonding network act as a transient proton acceptor at multiple points in the oxygen-evolving cycle.

  6. 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...

  7. The internal structure and dynamics of the railgun plasma armature between infinitely wide ablating rails

    Science.gov (United States)

    Frese, M. H.

    Conventional guns cannot achieve projectile velocities much greater than the sound speed in burned chemical propellants. Plasma armature railguns should not be subject to the same type of velocity limit. However, experiments indicate that there may be some other mechanism which can limit the velocity. A theory that accurately predicts the observed velocity limit could provide the insight necessary to raise or even lift that limit. As yet, there is no theoretical explanation drawn from physical first principles which predicts a limit to the achievable velocity. This report describes the first phase of an effort to use two-dimensional dynamic magnetohydrodynamic (MHD) simulation of the plasma motion in the bore to produce such an explanation. In this phase, MACH2, an Air Force two-dimensional MHD code has been quickly adapted to this problem. The principal goal of this effort was to demonstrate the feasibility and desirability of using MACH2 for railgun armature simulation. However, the simulations of plasma armatures described here are the most sophisticated models of the railgun arc presently available; they show the armature as a dynamic and developing plasma in a way never before seen. The goal could not have been more clearly achieved.

  8. 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

  9. Intramolecular resonance-assisted hydrogen bonds: A theoretical description by means of atomic charges and charge fluxes

    Science.gov (United States)

    Baranović, Goran

    2014-01-01

    The characterization of intramolecular H-bonds in terms of atomic charges and charge fluxes (at the B3LYP/cc-pVTZ level of theory) has been extended to the case of the so called resonance-assisted (RA) H-bonds. A quadratic correlation between the charge fluxes ϕH and the molecular IR absorption coefficients E that includes the entire family of the studied systems (31 of them) containing both intra- and intermolecular hydrogen bonds (O-H⋯O/N) confirmed the critical importance of the charge fluxes on the IR intensity enhancements. Since they reflect changing of the atomic charge distribution during the normal modes of vibrations, the dynamic nature of hydrogen bonding properties has been re-emphasized. The changes of the charge flux of the hydroxyl hydrogen in an RA intramolecular H-bond are between those for “free” OH bonds and the values calculated for intermolecular H-bonds. The transition “free” → intramolecular → intermolecular is gradual and therefore the hydrogen charge flux can be considered as practically sufficient to give quantitative measure to the intuitively obvious statement that “intramolecular H-bonding is somehow in between no H-bonding situation and intermolecular H-bonding” and thus provide a quantitative and yet simple parameterization of H-bond strength. In strictly planar molecules, the difference of the sums of charges of atoms participating in the 6-membered H-bond ring ΔΣ can serve as a measure of the charge delocalization after the H-bond is formed. The electronic charge is withdrawn from the group of six atoms when the H-bond is formed in nitrophenol (ΔΣ = -0.07), while the opposite is true (ΔΣ = +0.03) for 2-hydroxy benzylidene amine. The corresponding values of the geometrical resonance parameter Δ are 0.39 and 0.37, respectively, similar to those found for 2-hydroxy acetophenone and 2-hydroxy benzaldehyde. The extent of the π-electron delocalization as measured by the resonance parameter Δ does not follow

  10. New observations by visualizing age stratification and internal dynamics of freshwater lenses in heterogeneous media - laboratory experiments and numerical simulations

    Science.gov (United States)

    Stoeckl, L.; Dose, E.; Houben, G.; Himmelsbach, T.

    2012-12-01

    We performed a series of multi-tracer laboratory scale experiments in a transparent sand-box model to visualize (a) processes during the genesis of freshwater lenses and (b) their internal dynamics. For physical modeling an acrylic glass box was used to simulate a cross section of an island, similar to Stoeckl & Houben (2012). Degassed salt water with a density of 1023 kg/m3 was injected from the bottom, saturating the sand inside the model. Fluorescent tracer dyes uranine, eosine and indigotine were used to mark the infiltrating fresh water from the top. All experiments were filmed and analyzed using fast motion mode. We performed two different types of experimental set-up according to Vacher (1988): (1) Layers of different hydraulic conductivity: By filling the sand-box model with sand of different grain sizes, layers of different hydraulic conductivity could be simulated. (2) Recharge distribution: By recharging the island heterogeneously we could observe shifts in the geometry of the freshwater lens. A novel approach of using different tracer colors and varying them spatially and over time within the recharge waters allowed us to visualize and measure internal flow processes. Age stratification and flow paths could therefore be investigated. Moreover, a combination of temporal and spatial tracer color variation in one single experiment enabled us to measure flow velocities of freshwater movement. Additionally, by injecting small amounts of tracer in the salt water environment, movements near the interface between fresh- and saltwater could be observed. Using the finite element model FEFLOW we could model the density driven dynamics of our small scale freshwater lens, including its formation and the degradation after turning off the recharge water. This is important to fill the gap between our physical sand-box model and ongoing field investigations. The main focus of this work is the effects of climate change as well as geological and morphological

  11. 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.

  12. Local Turbulence Suppression and Flow Shear Dynamics During qmin-Triggered Internal Transport Barriers

    Science.gov (United States)

    Shafer, M. W.; McKee, G. R.; Schlossberg, D. J.; Austin, M. E.; Waltz, R. E.; Candy, J.

    2007-11-01

    Turbulence is observed to transiently decrease locally during the formation of internal transport barriers (ITBs) following the appearance of low-order rational qmin surfaces in negative central shear discharges on DIII-D. Simultaneously, increased poloidal flow shear is observed. To further study this phenomenon, localized 2D density fluctuation measurements of turbulence and turbulence flow were obtained over 0.3 < r/a < 0.7 via the high-sensitivity beam emission spectroscopy diagnostic. Both the reduction in fluctuations and the poloidal velocity shear are found to propagate radially outward at about 1 m/s. Initial observations suggest that these effects follow the q=2 surface. Related GYRO simulations suggest transient zonal flows form near the q=2 surface to trigger these ITBs. High-frequency poloidal velocity measurements will be used to examine this mechanism.

  13. 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.

  14. Summary of the structure and dynamics of international trade opportunities for new technologies

    Energy Technology Data Exchange (ETDEWEB)

    Watts, R.; Campbell, R.; Smith, S.; Sommers, P.

    1979-09-01

    This paper first provides a nomenclature and symbol system for describing the infrastructure that supports the export (or the import) of goods between countries. While the principal interest is in the export of high-technology goods to early foreign markets, the principles involved also apply to domestic commercialization of new technologies. The nomenclature-symbol system presented provides a schematic method of displaying complete relationships between actors and functions - an interaction matrix. A second aspect of the paper involves sketching out the need for further work to identify the motives, problems, and constraints of each key actor in international trade, particularly regarding new high-technology products. It is believed that the investigation should emphasize initial phases of market development when the behavior of actors does not appear to follow previous applications of microeconomic theory. Understanding this difference between theory and behavior could improve Federal efforts to commercialize new technologies. 18 references.

  15. International evidence on crude oil price dynamics. Applications of ARIMA-GARCH models

    Energy Technology Data Exchange (ETDEWEB)

    Mohammadi, Hassan [Department of Economics, Illinois State University, Normal, IL 61790-4200 (United States); Su, Lixian [Graduate Student, Department of Economics, Illinois State University, Normal, IL 61790-4200 (United States)

    2010-09-15

    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)

  16. 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.

  17. 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.

  18. Ion-molecule reactions of O,S-dimethyl methylphosphonothioate: evidence for intramolecular sulfur oxidation during VX perhydrolysis.

    Science.gov (United States)

    McAnoy, Andrew M; Williams, Jilliarne; Paine, Martin R L; Rogers, Michael L; Blanksby, Stephen J

    2009-12-18

    The alkaline perhydrolysis of the nerve agent O-ethyl S-[2-(diisopropylamino)ethyl] methylphosphonothioate (VX) was investigated by studying the ion-molecule reactions of HOO(-) with O,S-dimethyl methylphosphonothioate in a modified linear ion-trap mass spectrometer. In addition to simple proton transfer, two other abundant product ions are observed at m/z 125 and 109 corresponding to the S-methyl methylphosphonothioate and methyl methylphosphonate anions, respectively. The structure of these product ions is demonstrated by a combination of collision-induced dissociation and isotope-labeling experiments that also provide evidence for their formation by nucleophilic reaction pathways, namely, (i) S(N)2 at carbon to yield the S-methyl methylphosphonothioate anion and (ii) nucleophilic addition at phosphorus affording a reactive pentavalent intermediate that readily undergoes internal sulfur oxidation and concomitant elimination of CH(3)SOH to yield the methyl methylphosphonate anion. Consistent with previous solution phase observations of VX perhydrolysis, the toxic P-O cleavage product is not observed in this VX model system and theoretical calculations identify P-O cleavage to be energetically uncompetitive. Conversely, intramolecular sulfur oxidation is calculated to be extremely exothermic and kinetically accessible explaining its competitiveness with the facile gas phase proton transfer process. Elimination of a sulfur moiety deactivates the nerve agent VX and thus the intramolecular sulfur oxidation process reported here is also able to explain the selective perhydrolysis of the nerve agent to relatively nontoxic products.

  19. Molecular simulation of caloric properties of fluids modelled by force fields with intramolecular contributions: Application to heat capacities

    Science.gov (United States)

    Smith, William R.; Jirsák, Jan; Nezbeda, Ivo; Qi, Weikai

    2017-07-01

    The calculation of caloric properties such as heat capacity, Joule-Thomson coefficients, and the speed of sound by classical force-field-based molecular simulation methodology has received scant attention in the literature, particularly for systems composed of complex molecules whose force fields (FFs) are characterized by a combination of intramolecular and intermolecular terms. The calculation of a thermodynamic property for a system whose molecules are described by such a FF involves the calculation of the residual property prior to its addition to the corresponding ideal-gas property, the latter of which is separately calculated, either using thermochemical compilations or nowadays accurate quantum mechanical calculations. Although the simulation of a volumetric residual property proceeds by simply replacing the intermolecular FF in the rigid molecule case by the total (intramolecular plus intermolecular) FF, this is not the case for a caloric property. We describe the correct methodology required to perform such calculations and illustrate it in this paper for the case of the internal energy and the enthalpy and their corresponding molar heat capacities. We provide numerical results for cP, one of the most important caloric properties. We also consider approximations to the correct calculation procedure previously used in the literature and illustrate their consequences for the examples of the relatively simple molecule 2-propanol, CH3CH(OH)CH3, and for the more complex molecule monoethanolamine, HO(CH2)2NH2, an important fluid used in carbon capture.

  20. 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.

  1. SRM Internal Flow Tests and Computational Fluid Dynamic Analysis. Volume 3; Titan, ASRM, and Subscale Motor Analyses

    Science.gov (United States)

    1995-01-01

    A computational fluid dynamics (CFD) analysis has been performed on the aft slot region of the Titan 4 Solid Rocket Motor Upgrade (SRMU). This analysis was performed in conjunction with MSFC structural modeling of the propellant grain to determine if the flow field induced stresses would adversely alter the propellant geometry to the extent of causing motor failure. The results of the coupled CFD/stress analysis have shown that there is a continual increase of flow field resistance at the aft slot due to the aft segment propellant grain being progressively moved radially toward the centerline of the motor port. This 'bootstrapping' effect between grain radial movement and internal flow resistance is conducive to causing a rapid motor failure.

  2. 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

    :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......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...

  3. 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...

  4. Intermolecular electron transfer from intramolecular excitation and coherent acoustic phonon generation in a hydrogen-bonded charge-transfer solid

    Science.gov (United States)

    Rury, Aaron S.; Sorenson, Shayne; Dawlaty, Jahan M.

    2016-03-01

    Organic materials that produce coherent lattice phonon excitations in response to external stimuli may provide next generation solutions in a wide range of applications. However, for these materials to lead to functional devices in technology, a full understanding of the possible driving forces of coherent lattice phonon generation must be attained. To facilitate the achievement of this goal, we have undertaken an optical spectroscopic study of an organic charge-transfer material formed from the ubiquitous reduction-oxidation pair hydroquinone and p-benzoquinone. Upon pumping this material, known as quinhydrone, on its intermolecular charge transfer resonance as well as an intramolecular resonance of p-benzoquinone, we find sub-cm-1 oscillations whose dispersion with probe energy resembles that of a coherent acoustic phonon that we argue is coherently excited following changes in the electron density of quinhydrone. Using the dynamical information from these ultrafast pump-probe measurements, we find that the fastest process we can resolve does not change whether we pump quinhydrone at either energy. Electron-phonon coupling from both ultrafast coherent vibrational and steady-state resonance Raman spectroscopies allows us to determine that intramolecular electronic excitation of p-benzoquinone also drives the electron transfer process in quinhydrone. These results demonstrate the wide range of electronic excitations of the parent of molecules found in many functional organic materials that can drive coherent lattice phonon excitations useful for applications in electronics, photonics, and information technology.

  5. Excited-state intramolecular proton transfer molecules bearing o-hydroxy analogues of green fluorescent protein chromophore.

    Science.gov (United States)

    Chuang, Wei-Ti; Hsieh, Cheng-Chih; Lai, Chin-Hung; Lai, Cheng-Hsuan; Shih, Chun-Wei; Chen, Kew-Yu; Hung, Wen-Yi; Hsu, Yu-Hsiang; Chou, Pi-Tai

    2011-10-21

    o-Hydroxy analogues, 1a-g, of the green fluorescent protein chromophore have been synthesized. Their structures and electronic properties were investigated by X-ray single-crystal analyses, electrochemistry, and luminescence properties. In solid and nonpolar solvents 1a-g exist mainly as Z conformers that possess a seven-membered-ring hydrogen bond and undergo excited-state intramolecular proton transfer (ESIPT) reactions, resulting in a proton-transfer tautomer emission. Fluorescence upconversion dynamics have revealed a coherent type of ESIPT, followed by a fast vibrational/solvent relaxation (decay of a few to several tens of picoseconds was resolved in cyclohexane. Accordingly, the proton-transfer tautomer emission intensity is moderate (0.08 in 1e) to weak (∼10(-4) in 1a) in cyclohexane. The stronger intramolecular hydrogen bonding in 1g suppresses the rotation of the aryl-alkene bond, resulting in a high yield of tautomer emission (Φ(f) ≈ 0.2). In the solid state, due to the inhibition of exo-C(5)-C(4)-C(3) rotation, intense tautomer emission with a quantum yield of 0.1-0.9 was obtained for 1a-g. Depending on the electronic donor or acceptor strength of the substituent in either the HOMO or LUMO site, a broad tuning range of the emission from 560 (1g) to 670 nm (1a) has been achieved.

  6. Estimation of Intramolecular Hydrogen-bonding Energy via the Substitution Method

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    The intramolecular hydrogen-bonding energies for eighteen molecules were calculated based on the substitution method, and compared with those predicted by the cis-trans method.The energy values obtained from two methods are close to each other with a correlation coefficient of 0.96.Furthermore, the hydrogen-bonding energies based on the substitution method are consistent with the geometrical features of intramolecular hydrogen bonds.Both of them demonstrate that the substitution method is capable of providing a good estimation of intramolecular hydrogen-bonding energy.

  7. Molecular dynamics simulation of SnF2 nanostructures in the internal channels of single-walled carbon nanotubes

    Science.gov (United States)

    Gotlib, I. Yu.; Ivanov-Schitz, A. K.; Murin, I. V.; Petrov, A. V.; Romantsov, G. A.; Zakalyukin, R. M.

    2014-07-01

    A molecular dynamics simulation of solid tin(II) fluoride nanostructures formed in internal channels of single-walled carbon nanotubes (SWCNTs) has been performed using two types of model potentials—without and with inclusion of the polarization of ions. For the potential taking into account the polarization of ions, an ordered SnF2@SWCNT structure is reproduced: in SWCNT(10, 10), it has the form of the SnF2 internal nanotube. At the same time, the SnF2@SWCNT(11,11) structure is substantially disordered (glass-like). It has been found that heating of the SnF2@SWCNT model system produces a superionic state characterized by a high mobility of fluorine ions without migration of tin ions. The model potentials disregard the covalent character of Sn-F bonds and the specific interactions of a lone electron pair of the Sn2+ ion. This makes it impossible to completely reproduce the properties of SnF2 at normal pressures. However, some characteristics of the SnF2 high-pressure modification can be reproduced if the polarization of ions is taken into account.

  8. On the importance of modelling the internal spatial dynamics of biological cells.

    Science.gov (United States)

    Sayyid, Faiz; Kalvala, Sara

    2016-07-01

    Spatial effects such as cell shape have very often been considered negligible in models of cellular pathways, and many existing simulation infrastructures do not take such effects into consideration. Recent experimental results are reversing this judgement by showing that very small spatial variations can make a big difference in the fate of a cell. This is particularly the case when considering eukaryotic cells, which have a complex physical structure and many subtle control mechanisms, but bacteria are also interesting for the huge variation in shape both between species and in different phases of their lifecycle. In this work we perform simulations that measure the effect of three common bacterial shapes on the behaviour of model cellular pathways. To perform these experiments we develop ReDi-Cell, a highly scalable GPGPU cell simulation infrastructure for the modelling of cellular pathways in spatially detailed environments. ReDi-Cell is validated against known-good simulations, prior to its use in new work. We then use ReDi-Cell to conduct novel experiments that demonstrate the effect that three common bacterial shapes (Cocci, Bacilli and Spirilli) have on the behaviour of model cellular pathways. Pathway wavefront shape, pathway concentration gradients, and chemical species distribution are measured in the three different shapes. We also quantify the impact of internal cellular clutter on the same pathways. Through this work we show that variations in the shape or configuration of these common cell shapes alter model cell behaviour.

  9. 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.

  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. Dynamic Analysis of Tunnel in Weathered Rock Subjected to Internal Blast Loading

    Science.gov (United States)

    Tiwari, Rohit; Chakraborty, Tanusree; Matsagar, Vasant

    2016-11-01

    The present study deals with three-dimensional nonlinear finite element (FE) analyses of a tunnel in rock with reinforced concrete (RC) lining subjected to internal blast loading. The analyses have been performed using the coupled Eulerian-Lagrangian analysis tool available in FE software Abaqus/Explicit. Rock and RC lining are modeled using three-dimensional Lagrangian elements. Beam elements have been used to model reinforcement in RC lining. Three different rock types with different weathering conditions have been used to understand the response of rock when subjected to blast load. The trinitrotoluene (TNT) explosive and surrounding air have been modeled using the Eulerian elements. The Drucker-Prager plasticity model with strain rate-dependent material properties has been used to simulate the stress-strain response of rock. The concrete damaged plasticity model and Johnson-Cook plasticity model have been used for the simulation of stress-strain response of concrete and steel, respectively. The explosive (TNT) has been modeled using Jones-Wilkins-Lee (JWL) equation of state. The analysis results have been studied for stresses, deformation and damage of RC lining and the surrounding rock. It is observed that damage in RC lining results in higher stress in rock. Rocks with low modulus and high weathering conditions show higher attenuation of shock wave. Higher amount of ground shock wave propagation is observed in case of less weathered rock. Ground heave is observed under blast loading for tunnel close to ground surface.

  12. Intramolecular and intermolecular hydrogen-bonding effects on photophysical properties of 2'-aminoacetophenone and its derivatives in solution.

    Science.gov (United States)

    Shimada, Hirofumi; Nakamura, Akihito; Yoshihara, Toshitada; Tobita, Seiji

    2005-04-01

    Effects of intra- and intermolecular hydrogen-bonds on the photophysical properties of 2'-aminoacetophenone derivatives (X-C6H4-COCH3) having a substituted amino group (X) with different hydrogen-bonding ability to the carbonyl oxygen (X: NH2(AAP), NHCH3(MAAP), N(CH3)2(DMAAP), NHCOCH3(AAAP), NHCOCF3(TFAAP)) are investigated by means of steady-state and time-resolved fluorescence spectroscopy and time-resolved thermal lensing. Based on the photophysical parameters obtained in aprotic solvents with different polarity and protic solvents with different hydrogen-bonding ability, the characteristic photophysical behavior of the 2'-aminoacetophenone derivatives is discussed in terms of hydrogen-bonding and n,pi*-pi,pi* vibronic coupling. The dominant deactivation process of AAP and MAAP in nonpolar aprotic solvents is the extremely fast internal conversion (k(ic)= 1.0 x 10(11) s(-1) for AAP and 3.9 x 10(10) s(-1) for MAAP in n-hexane). The internal conversion rates of both compounds decrease markedly with increasing solvent polarity, suggesting that vibronic interactions between close-lying S1(pi,pi*) and S2(n,pi*) states lead to the large increase in the non-radiative decay rate of the lowest excited singlet state. It is also suggested that for MAAP, which has a stronger hydrogen-bond as compared to AAP, an intramolecular hydrogen-bonding induced deactivation is involved in the dissipation of the S1 state. For DMAAP, which cannot possess an intramolecular hydrogen-bond, the primary relaxation mechanism of the S1 state in nonpolar aprotic solvents is the intersystem crossing to the triplet state, whereas in protic solvents very efficient internal conversion due to intermolecular hydrogen-bonding is induced. In contrast, the fluorescence spectra of AAAP and TFAAP, which have an amino group with a much stronger hydrogen-bonding ability, give strongly Stokes-shifted fluorescence, indicating that these compounds undergo excited-state intramolecular proton transfer reaction

  13. A discrete chemo-dynamical model of the dwarf spheroidal galaxy Sculptor: mass profile, velocity anisotropy and internal rotation

    CERN Document Server

    Zhu, Ling; Watkins, Laura L; Posti, Lorenzo

    2016-01-01

    We present a new discrete chemo-dynamical axisymmetric modeling technique, which we apply to the dwarf spheroidal galaxy Sculptor. The major improvement over previous Jeans models is that realistic chemical distributions are included directly in the dynamical modelling of the discrete data. This avoids loss of information due to spatial binning and eliminates the need for hard cuts to remove contaminants and to separate stars based on their chemical properties. Using a combined likelihood in position, metallicity and kinematics, we find that our models naturally separate Sculptor stars into a metal-rich and a metal-poor population. Allowing for non-spherical symmetry, our approach provides a central slope of the dark matter density of $\\gamma = 0.5 \\pm 0.3$. The metal-rich population is nearly isotropic (with $\\beta_r^{red} = 0.0\\pm0.1$) while the metal-poor population is tangentially anisotropic (with $\\beta_r^{blue} = -0.2\\pm0.1$) around the half light radius of $0.26$ kpc. A weak internal rotation of the m...

  14. Systemic risk and causality dynamics of the world international shipping market

    Science.gov (United States)

    Zhang, Xin; Podobnik, Boris; Kenett, Dror Y.; Eugene Stanley, H.

    2014-12-01

    Various studies have reported that many economic systems have been exhibiting an increase in the correlation between different market sectors, a factor that exacerbates the level of systemic risk. We measure this systemic risk of three major world shipping markets, (i) the new ship market, (ii) the second-hand ship market, and (iii) the freight market, as well as the shipping stock market. Based on correlation networks during three time periods, that prior to the financial crisis, during the crisis, and after the crisis, minimal spanning trees (MSTs) and hierarchical trees (HTs) both exhibit complex dynamics, i.e., different market sectors tend to be more closely linked during financial crisis. Brownian distance correlation and Granger causality test both can be used to explore the directional interconnectedness of market sectors, while Brownian distance correlation captures more dependent relationships, which are not observed in the Granger causality test. These two measures can also identify and quantify market regression periods, implying that they contain predictive power for the current crisis.

  15. Internal Representation of Task Rules by Recurrent Dynamics: The Importance of the Diversity of Neural Responses

    Science.gov (United States)

    Rigotti, Mattia; Rubin, Daniel Ben Dayan; Wang, Xiao-Jing; Fusi, Stefano

    2010-01-01

    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. PMID:21048899

  16. High-Speed Rotor Analytical Dynamics on Flexible Foundation Subjected to Internal and External Excitation

    Directory of Open Access Journals (Sweden)

    Jivkov Venelin S.

    2016-12-01

    Full Text Available The paper presents a geometrical approach to dynamics simulation of a rigid and flexible system, compiled of high speed rotating machine with eccentricity and considerable inertia and mass. The machine is mounted on a vertical flexible pillar with considerable height. The stiffness and damping of the column, as well as, of the rotor bearings and the shaft are taken into account. Non-stationary vibrations and transitional processes are analyzed. The major frequency and modal mode of the flexible column are used for analytical reduction of its mass, stiffness and damping properties. The rotor and the foundation are modelled as rigid bodies, while the flexibility of the bearings is estimated by experiments and the requirements of the manufacturer. The transition effects as a result of limited power are analyzed by asymptotic methods of averaging. Analytical expressions for the amplitudes and unstable vibrations throughout resonance are derived by quasi-static approach increasing and decreasing of the exciting frequency. Analytical functions give the possibility to analyze the influence of the design parameter of many structure applications as wind power generators, gas turbines, turbo-generators, and etc. A numerical procedure is applied to verify the effectiveness and precision of the simulation process.

  17. SRM Internal Flow Test and Computational Fluid Dynamic Analysis. Volume 1; Major Task Summaries

    Science.gov (United States)

    Whitesides, R. Harold; Dill, Richard A.; Purinton, David C.

    1995-01-01

    During the four year period of performance for NASA contract, NASB-39095, ERC has performed a wide variety of tasks to support the design and continued development of new and existing solid rocket motors and the resolution of operational problems associated with existing solid rocket motor's at NASA MSFC. This report summarizes the support provided to NASA MSFC during the contractual period of performance. The report is divided into three main sections. The first section presents summaries for the major tasks performed. These tasks are grouped into three major categories: full scale motor analysis, subscale motor analysis and cold flow analysis. The second section includes summaries describing the computational fluid dynamics (CFD) tasks performed. The third section, the appendices of the report, presents detailed descriptions of the analysis efforts as well as published papers, memoranda and final reports associated with specific tasks. These appendices are referenced in the summaries. The subsection numbers for the three sections correspond to the same topics for direct cross referencing.

  18. 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.

  19. A study of internal energy relaxation in shocks using molecular dynamics based models

    Energy Technology Data Exchange (ETDEWEB)

    Li, Zheng, E-mail: zul107@psu.edu; Parsons, Neal, E-mail: neal.parsons@cd-adapco.com [Department of Aerospace Engineering, The Pennsylvania State University, University Park, Pennsylvania 16802 (United States); Levin, Deborah A., E-mail: deblevin@illinois.edu [Department of Aerospace Engineering, University of Illinois Urbana-Champaign, Urbana, Illinois 61801-2935 (United States)

    2015-10-14

    Recent potential energy surfaces (PESs) for the N{sub 2} + N and N{sub 2} + N{sub 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{sub 2} + N{sub 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{sub 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.

  20. The intramolecular charge transfer state in carbonyl-containing polyenes and carotenoids.

    Science.gov (United States)

    Enriquez, Miriam M; Fuciman, Marcel; LaFountain, Amy M; Wagner, Nicole L; Birge, Robert R; Frank, Harry A

    2010-09-30

    Numerous femtosecond time-resolved optical spectroscopic experiments have reported that the lifetime of the low-lying S(1) state of carbonyl-containing polyenes and carotenoids decreases with increasing solvent polarity. The effect becomes even more pronounced as the number of double bonds in the conjugated π-electron system decreases. The effect has been attributed to an intramolecular charge transfer (ICT) state coupled to S(1), but it is still not clear what the precise molecular nature of this state is, and how it is able to modulate the spectral and dynamic properties of polyenes and carotenoids. In this work, we examine the nature of the ICT state in three substituted polyenes: crocetindial, which contains two terminal, symmetrically substituted carbonyl groups in conjugation with the π-electron system, 8,8'-diapocarotene-8'-ol-8-al, which has one terminal conjugated carbonyl group and one hydroxyl group, and 8,8'-diapocarotene-8,8'-diol, which has two terminal, symmetrically positioned, hydroxyl groups but no carbonyls. Femtosecond time-resolved optical spectroscopic experiments on these molecules reveal that only the asymmetrically substituted 8,8'-diapocarotene-8'-ol-8-al exhibits any substantial effect of solvent on the excited state spectra and dynamics. The data are interpreted using molecular orbital theory which shows that the ICT state develops via mixing of the low-lying S(1) (2(1)A(g)-like) and S(2) (1(1)B(u)-like) excited singlet states to form a resultant state that preferentially evolves in polar solvent and exhibits a very large (∼25 D) dipole moment. Molecular dynamics calculations demonstrate that the features of the ICT state are present in ∼20 fs.

  1. Solvent effect on intramolecular electron transfer rates of mixed-valence biferrocene monocation derivatives.

    Science.gov (United States)

    Masuda, Y; Shimizu, C

    2006-06-01

    Intramolecular electron transfer (ET) rates in various solvents of mixed-valence biferrocene monocation (Fe(II), Fe(III)) and the 1',1' ''-diiodo and 1',1' ''-diethyl derivatives (respectively abbreviated as BFC(+), I(2)BFC(+), and Et(2)BFC(+)) were determined by means of the spin-lattice relaxation times of the protons, taking into account the local magnetic field fluctuation caused by the electron hopping between the two ferrocene units. We also determined the ET rates of a mixed-valence diferrocenylacetylene monocation (DFA(+)) in order to examine the effect of the insertion of an acetylene bridge between the two ferrocene units. The insertion of the bridge decreased the ET rate, while the effect of substitution on the cyclopentadienyl rings on the rate was minor. The observed rates for each mixed-valence monocation in various solvents did not correlate with the reorganization energies, but we did find a significant contribution of the solvent dynamics. The observed rates were considerably higher than those expected on the basis of the Sumi-Marcus-Nalder model in which the solvents were regarded as dielectric continua. The slope of the logarithm plot of the pre-exponential factors in various solvents for each mixed-valence monocation versus the inverse of the longitudinal dielectric relaxation times of the solvents was significantly smaller than unity, and the slope for DFA(+) was larger than those for BFC(+), I(2)BFC(+), and Et(2)BFC(+). These results were ascribed to a partial contribution of the dielectric friction to the dynamics along the solvent coordinate; the extent of the contribution decreased with a reduction in the ET distance. For the dynamics along the solvent coordinate of the ET reactions in methanol, the observed rates indicated an important contribution by the minor dielectric relaxation components with faster relaxation times, rather than the major component with an extraordinarily long relaxation time.

  2. Slow Intramolecular Vibrational Relaxation Leads to Long-Lived Excited-State Wavepackets.

    Science.gov (United States)

    Rafiq, Shahnawaz; Scholes, Gregory D

    2016-09-01

    Broadband optical pump and compressed white light continuum probe were used to measure the transient excited-state absorption, ground-state bleach, and stimulated emission signals of cresyl violet solution in methanol. Amplitude oscillations caused by wavepacket motion in the ground and excited electronic states were analyzed. It was found that vibrational coherences in the excited state persist for more than the experimental waiting time window of 6 ps, and the strongest mode had a dephasing time constant of 2.4 ps. We hypothesize the dephasing of the wavepacket in the excited state is predominantly caused by intramolecular vibrational relaxation (IVR). Slow IVR indicates weak mode-mode coupling and therefore weak anharmonicity of the potential of this vibration. Thus, the initially prepared vibrational wavepacket in the excited state is not significantly perturbed by nonadiabatic coupling to other electronic states, and hence the diabatic and adiabatic representations of the system are essentially identical within the Born-Oppenheimer approximation. The wavepacket therefore evolves with time in an almost harmonic potential, slowly dephased by IVR and the pure vibrational decoherence. The consistency in the position of node (phase change in the wavepacket) in the excited-state absorption and stimulated emission signals without undergoing any frequency shift until the wavepacket is completely dephased conforms to the absence of any reactive internal conversion.

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

    Science.gov (United States)

    Mortensen, Kim I.; Sung, Jongmin; Flyvbjerg, Henrik; Spudich, James A.

    2015-10-01

    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 and using only simple means, we simultaneously determine both the relative (x,y)-separation of the fluorophores and their individual orientations in space with accuracy and precision. The positions and orientations of two domains of the same molecule are thus time-resolved. Using short double-stranded DNA molecules internally labelled with two fixed fluorophores, we demonstrate the accuracy and precision of our method using the known structure of double-stranded DNA as a benchmark, resolve 10-base-pair differences in fluorophore separations, and determine the unique 3D orientation of each DNA molecule, thereby establishing short, double-labelled DNA molecules as probes of 3D orientation of anything to which one can attach them firmly.

  4. Multi-objective optimization of internal combustion engine by means of 1D fluid-dynamic models

    Energy Technology Data Exchange (ETDEWEB)

    D' Errico, G.; Cerri, T.; Pertusi, G. [Dipartimento di Energia, Politecnico di Milano, Via Lambruschini 4, 20156 Milan (Italy)

    2011-03-15

    The definition of an efficient optimization methodology for internal combustion engine design using 1D fluid dynamic simulation models is presented. This work aims at discussing the fundamental numerical and fluid dynamic aspects which can lead to the definition of a best practice technique, depending on the complexity of the problem to be dealt with, on the number of design parameters, objective variables and constrains. For these reasons, both single-and multi-objective problems will be addressed, where the former are still of relevant interest (i.e. optimization of engine performances), while the latter have a much wider range of applications and are often characterized by conflicting objectives. The Mesh Adaptive Direct Search (MADS) was chosen among the class of direct search methods and compared with the Genetic Algorithms to solve single-objective problems, and similarly two different algorithms were chosen and compared to solve multi-objective problems: the {epsilon}-constraint method and the NSGA-II (Non-Dominated Sorting Genetic Algorithm). A single cylinder spark ignition engine, used in a motorbike application, was chosen as test case, to allow reduced computational times, without any loss of generality of the results. The analysis evaluate the convergence and efficiency of each methodology for the different problems which are solved. The achieved goal is not the definition of an ever valid mathematical strategy, but here focus is given on the parallel application of a detailed fluid dynamic analysis and automated optimization techniques to suggest a best practice technique to be employed depending on the characteristic of the optimization problem to be solved. (author)

  5. Molecular dynamics simulation and vibrational spectroscopy of molecules (Ⅰ)——A method of internal coordinate correlation for band assignment

    Institute of Scientific and Technical Information of China (English)

    杨小震

    1995-01-01

    A method of simulation of vibrational spectra by using the "internal coordinatecorrelation" based on molecular dynamics algorithms and auto-correlation function has been developed.The in-ternal coordinates,such as bond stretching,bond angle bending,out-of-plane bending and torsion,are treatedas the dynamic variables to obtain a density spectrum or the "internal coordinate correlation" spectrum Theadvantages of this method are as follows:i)it is easier to assign vibration modes for the density spectra;ii)itsimply connects the Fourier transformed "internal coordinate correlation" function to the eigenvectors innormal coordinate analysis;iii)it is a basis for simulating IR and Raman active spectra of a large molecularsystem.

  6. Glutathione-coordinated [2Fe-2S] cluster is stabilized by intramolecular salt bridges.

    Science.gov (United States)

    Li, Jingwei; Pearson, Stephen A; Fenk, Kevin D; Cowan, J A

    2015-12-01

    Halide salts of alkali and alkaline earth metals were used to probe the contributions of intramolecular salt bridge formation on the stability of glutathione-coordinated [2Fe-2S] cluster toward hydrolysis. The effect of ionic strength on cluster stability was quantitatively investigated by application of Debye-Hückel theory to the rates of hydrolysis. Results from this study demonstrate that ionic strength influences the stability of the cluster, with the rate of cluster degradation depending on the charge density, hydrated ionic radius, and hydration energy. The identity of the salt ions was also observed to be correlated with the binding affinity toward the cluster. Based on the modified Debye-Hückel equation and counterion screening effect, these results suggest that interactions between glutathione molecules in the [2Fe-2S](GS)4 cluster is via salt bridges, in agreement with our previous results where modifications of glutathione carboxylates and amines prevented solution aggregation and cluster formation. These results not only provide a rationale for the stability of such clusters under physiological conditions, but also suggest that the formation of glutathione-complexed [2Fe-2S] cluster from a glutathione tetramer may be facilitated by salt bridge interactions between glutathione molecules prior to cluster assembly, in a manner consistent with Nature's equivalent of dynamic combinatorial chemistry.

  7. Femtosecond Heterodyne Transient Grating Spectroscopic Studies of Intramolecular Charge Transfer Character of Peridinin and Peridinin Analogs

    Science.gov (United States)

    Bishop, Michael; Khosravi, Soroush; Obaid, Razib; Whitelock, Hope; Carroll, Ann Marie; Lafountain, Amy; Frank, Harry; Beck, Warren; Gibson, George; Berrah, Nora

    2016-05-01

    The peridinin chlorophyll-a protein is a light harvesting complex found in several species of dinoflagellates. Peridinin absorbs strongly in the mid-visible spectral region and, despite the lack of a strong permanent dipole moment in its lowest energy excited state, is able to transfer excitation energy quickly and efficiently to chlorophyll-a. It is believed that the high efficiency arises from the development of intramolecular charge-transfer (ICT) character upon photoexcitation. Recently, heterodyne transient grating spectroscopy has been used to study the ultrafast (<50 fs) dynamics of β carotene and peridinin. The studies show evidence for a structurally displaced intermediate in both cases and strong ICT character in the case of peridinin, but up to now the work has not provided appropriate control experiments. The present experiments examine peridinin and two peridinin analogs, S1-peridinin and S2-peridinin. S1-peridinin is reported to have greatly diminished ICT character, and S2-peridinin is reported to have little-or-no ICT character. Heterodyne transient grating data will be presented and provide a more unambiguous characterization spectral and kinetic properties associated with the peridinin ICT state. Funded by the DoE-BES, Grant No. DE-SC0012376.

  8. 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.

  9. Effect of loop on the stability of intramolecular triplex DNA

    Institute of Scientific and Technical Information of China (English)

    杨林静; 白春礼; 李任植; 汪新文; 王琛

    1997-01-01

    Conformation stabilities of intramolecular triple-helical DNAs (intra-tnplex DNAs: 5-d(TC)6-d(T)m-d(CT)6-d(C)n-d(AG)6-3’,where m and n are chosen to be 4 and 3) have been examined by molecular mechanics.The four intra-triplexes (H-DNAs) are compared with the mtermolecular triplexes d(TC)6 * d ( AG)6 d(CT)6.The results revealed that loops do not significantly influence the mtratriplex conformations,loop conformations,however,depend partly on its length.Loop also makes strand Ⅱ of every intra-triplex DNA longer than that of the inter-triplex DNA.Most of residue sugar conformations of triple-helical DNAs are S-type,there aiso exist,however,N-type conformation and the conformations between S-type and N-type Possible models of the five triplex DNAs are presented.

  10. Intramolecular charge transfer effects on 3-aminobenzoic acid

    Energy Technology Data Exchange (ETDEWEB)

    Stalin, T. [Department of Chemistry, Annamalai University, Annamalainagar, Chidambaram 608 002, Tamil Nadu (India); Rajendiran, N. [Department of Chemistry, Annamalai University, Annamalainagar, Chidambaram 608 002, Tamil Nadu (India)], E-mail: drrajendiran@rediffmail.com

    2006-03-20

    Effect of solvents, buffer solutions of different pH and {beta}-cyclodextrin on the absorption and fluorescence spectra of 3-aminobenzoic acid (3ABA) have been investigated. The solid inclusion complex of 3ABA with {beta}-CD is discussed by UV-Vis, fluorimetry, semiempirical quantum calculations (AM1), FT-IR, {sup 1}H NMR and Scanning Electron Microscope (SEM). The thermodynamic parameters ({delta}H, {delta}G and {delta}S) of the inclusion process are also determined. The experimental results indicated that the inclusion processes is an exothermic and spontaneous. The large Stokes shift emission in solvents with 3ABA are correlated with different solvent polarity scales suggest that, 3ABA molecule is more polar in the S{sub 1} state. Solvent, {beta}-CD studies and excited state dipole moment values confirms that the presence of intramolecular charge transfer (ICT) in 3ABA. Acidity constants for different prototropic equilibria of 3ABA in the S{sub 0} and S{sub 1} states are calculated. {beta}-Cyclodextrin studies shows that 3ABA forms a 1:1 inclusion complex with {beta}-CD. {beta}-CD studies suggest COOH group present in non-polar part and amino group present in hydrophilic part of the {beta}-CD cavity. A mechanism is proposed to explain the inclusion process.

  11. Photoinduced intermolecular and intramolecular actions between eosin and porphyrin

    Institute of Scientific and Technical Information of China (English)

    何建军; 张曼华; 沈涛

    1997-01-01

    Two dyads of eosin and porphyrin linked with a semi-rigid (-CH2phCH2-) or flexible (-(CH2)4-) bridge and their reference model compounds were synthesized and characterized The intermoleccular interaction and intramolecular photoinduced singlet energy transfer and electron transfer were studied by their absorp tion spectra,fluorescence emission,excitation spectra and fluorescence lifetime The model compounds,ethyl ester of eosm (EoEt) and porphyrin (PorEt),could form complexes in the ground state.When the eosin moieties in dyads were excited,they could transfer some singlet energy to the porphyrins; in the meantime,they could also ndsce electron transfer between two chromophores.Exciting the porphyrin moieties in dyads could induce electron transfer from eosin moieties to porphyrin moieties.The efficiencies (EnT,ET) and rate constants (kEnT,kET) were related to the polarity of solvents and mutual orientation of the two chromophores in dyads.

  12. Aspects of organochalcogen (S, Se, Te) compounds stabilized by intramolecular coordination

    Indian Academy of Sciences (India)

    G Mugesh; Arunashree Panda; Harkesh B Singh

    2000-06-01

    The application of intramolecular coordination in the isolation of novel diaryl diselenides and their derivatives, monomeric chalcogenolato complexes of group 12 metals, glutathione peroxidase mimics, hybrid bi-, tri- and multidentate ligands and selenium-containing azamacrocycles is described.

  13. THEORY OF INTRAMOLECULAR ORIENTATIONAL ORDER OF MESOGENIC UNITS IN MC-LCPS AND ITS APPLICATION

    Institute of Scientific and Technical Information of China (English)

    WANG Xiaogong; LIU Deshan; ZHOU Qixiang

    1993-01-01

    New concepts such as intramolecular orientational order parameter and corresponding model as well as theory were proposed to describe the intramolecular orientation of mesogenic units in the liquid crystalline polymer chains. The relationship between the intramolecular orientational order parameter and the molecular geometrical parameters such as the bond angle, the bond rotational angle and the rotational potential energy of chemical bonds was deduced. A significant even-odd oscillation of the intramolecular orientational order parameter of LCPs with different length of flexible spacer was found and rationally related to even-odd zigzag manner of transition properties. The verification and application of the theory are also discussed. The isotropic transition temperature predicted by the theory is shown to be in favourable agreement with the experiments.

  14. 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

  15. Tree-ring cellulose exhibits several distinct intramolecular 13C signals

    Science.gov (United States)

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

    2017-04-01

    Stable carbon isotopes are a key tool in biogeosciences. Present applications including compound-specific isotope analysis measure 13C/12C ratios (δ13C) of bulk material or of whole molecules. However, it is well known that primary metabolites also show large intramolecular 13C variation - also called isotopomer variation. This variation reflects 13C fractionation by enzyme reactions and therefore encodes metabolic information. Furthermore, δ13C must be considered an average of the intramolecular 13C distribution. Here we will present (1) methodology to analyse intramolecular 13C distributions of tree-ring cellulose by quantitative 13C NMR (Chaintreau et al., 2013, Anal Chim Acta, 788, 108-113); (2) intramolecular 13C distributions of an annually-resolved tree ring chronology (Pinus nigra, 1961-1995); (3) isotope parameters and terminology for analysis of intramolecular isotope time series; (4) a method for correcting for heterotrophic C redistribution. We will show that the intramolecular 13C distribution of tree-ring cellulose shows large variation, with differences between isotopomers exceeding 10‰Ṫhus, individual 13C isotopomers of cellulose constitute distinct 13C inputs into major global C pools such as wood and soil organic matter. When glucose units with the observed intramolecular 13C pattern are broken down along alternative catabolic pathways, it must be expected that respired CO2 with strongly differing δ13C will be released; indicating that intramolecular 13C variation affects isotope signals of atmosphere-biosphere C exchange fluxes. taking this variation into account will improve modelling of the global C cycle. Furthermore, cluster analysis shows that tree-ring glucose exhibits several independent intramolecular 13C signals, which constitute distinct ecophysiological information channels. Thus, whole-molecule 13C analysis likely misses a large part of the isotope information stored in tree rings. As we have shown for deuterium (Ehlers et al

  16. 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 the N-protecting group influenced the yield and selectivity of the reactions. Most strikingly, intramolecular hydrovinylation allowed the preparation of diastereomerically pure bicyclic amines as e.g. hexahydroindoles 2a-2d....

  17. Asymmetric Intramolecular Alkylation of Chiral Aromatic Imines via Catalytic C-H Bond Activation

    Energy Technology Data Exchange (ETDEWEB)

    Watzke, Anja; Wilson, Rebecca; O' Malley, Steven; Bergman, Robert; Ellman, Jonathan

    2007-04-16

    The asymmetric intramolecular alkylation of chiral aromatic aldimines, in which differentially substituted alkenes are tethered meta to the imine, was investigated. High enantioselectivities were obtained for imines prepared from aminoindane derivatives, which function as directing groups for the rhodium-catalyzed C-H bond activation. Initial demonstration of catalytic asymmetric intramolecular alkylation also was achieved by employing a sterically hindered achiral imine substrate and catalytic amounts of a chiral amine.

  18. Surface-induced intramolecular electron transfer in multi-centre redox metalloproteins: the di-haem protein cytochrome c4 in homogeneous solution and at electrochemical surfaces

    Science.gov (United States)

    Chi, Qijin; Zhang, Jingdong; Jensen, Palle S.; Nazmudtinov, Renat R.; Ulstrup, Jens

    2008-09-01

    Intramolecular electron transfer (ET) between transition metal centres is a core feature of biological ET and redox enzyme function. The number of microscopic redox potentials and ET rate constants is, however, mostly prohibitive for experimental mapping, but two-centre proteins offer simple enough communication networks for complete mapping to be within reach. At the same time, multi-centre redox proteins operate in a membrane environment where conformational dynamics and ET patterns are quite different from the conditions in a homogeneous solution. The bacterial respiratory di-haem protein Pseudomonas stutzeri cytochrome c4 offers a prototype target for environmental gating of intra-haem ET. ET between P. stutzeri cyt c4 and small molecular reaction partners in solution appears completely dominated by intermolecular ET of each haem group/protein domain, with no competing intra-haem ET, for which accompanying propionate-mediated proton transfer is a further barrier. The protein can, however, be immobilized on single-crystal, modified Au(111) electrode surfaces with either the low-potential N terminal or the high-potential C terminal domain facing the surface, clearly with fast intramolecular ET as a key feature in the electrochemical two-ET process. This dual behaviour suggests a pattern for multi-centre redox metalloprotein function. In a homogeneous solution, which is not the natural environment of cyt c4, the two haem group domains operate largely independently with conformations prohibitive for intramolecular ET. Binding to a membrane or electrochemical surface, however, triggers conformational opening of intramolecular ET channels. The haem group orientation in P. stutzeri cyt c4 is finally noted to offer a case for orientation dependent electronic rectification between a substrate and a tip in electrochemical in situ scanning tunnelling microscopy or nanoscale electrode configurations.

  19. Tuning the role of charge-transfer states in intramolecular singlet exciton fission through side-group engineering

    Science.gov (United States)

    Lukman, Steven; Chen, Kai; Hodgkiss, Justin M.; Turban, David H. P.; Hine, Nicholas D. M.; Dong, Shaoqiang; Wu, Jishan; Greenham, Neil C.; Musser, Andrew J.

    2016-12-01

    Understanding the mechanism of singlet exciton fission, in which a singlet exciton separates into a pair of triplet excitons, is crucial to the development of new chromophores for efficient fission-sensitized solar cells. The challenge of controlling molecular packing and energy levels in the solid state precludes clear determination of the singlet fission pathway. Here, we circumvent this difficulty by utilizing covalent dimers of pentacene with two types of side groups. We report rapid and efficient intramolecular singlet fission in both molecules, in one case via a virtual charge-transfer state and in the other via a distinct charge-transfer intermediate. The singlet fission pathway is governed by the energy gap between singlet and charge-transfer states, which change dynamically with molecular geometry but are primarily set by the side group. These results clearly establish the role of charge-transfer states in singlet fission and highlight the importance of solubilizing groups to optimize excited-state photophysics.

  20. Steric effects on intramolecular reactivity in cyclic dipeptides: Conformational analysis validated by a combined MD/DFT approach

    Science.gov (United States)

    Lewandowska, A.; Carmichael, I.; Hörner, G.; Hug, G. L.; Marciniak, B.

    2011-08-01

    The present Molecular Dynamics (MD) simulation study addresses the geometric requirements of close-contact formation in short peptides. This process, that is probed herein by intramolecular H-atom transfer, initiated by triplet-excited ketones, demands close contact between the H-donating and H-accepting moieties. Thus, any deduction about the compound's reactivity based just on MD simulations, requires independent verification of the computed conformational preferences. In this study, a procedure was developed using diketopiperazine-linked benzophenone/tyrosine dyads. Specifically, it involves a comparison of the dyads' experimental 3J(H α-H β(a/b)) spin-spin coupling constants with the theoretical values obtained by weighting DFT-computed spin-spin coupling constants with the MD-computed probability distributions for the dyads' configurations.

  1. Intramolecular proton or hydrogen-atom transfer in the ground- and excited-states of 2-hydroxybenzophenone: A theoretical study

    Energy Technology Data Exchange (ETDEWEB)

    Yi, Ping G. [School of Chemistry and Chemical Engineering, Hunan University of Science and Technology, Xiangtan 411201 (China); Liang, Yong H. [School of Chemistry and Chemical Engineering, Hunan University of Science and Technology, Xiangtan 411201 (China)], E-mail: kaixgl@sina.com.cn; Cao, Chen Z. [School of Chemistry and Chemical Engineering, Hunan University of Science and Technology, Xiangtan 411201 (China)

    2005-08-29

    The internal rotational motion and the ground- and excited-state intramolecular proton transfer (GISPT, EISPT) reaction of 2-hydroxybenzophenone (HBP) are studied at the B3LYP/6-31G**, CIS/6-31G** and TD B3LYP/6-31++G** level. The calculated results show that there is only one minimum at the S{sub 0} and S{sub 1} state, the enol form (E) is the single minimum at the S{sub 0} state, and its rotamers and tautomers are with more than 8.24 and 10.43 kcal/mol less stable, respectively, however, the keto tautomer (K*) is the single minimum at the S{sub 1} state. Therefore, the ground- and excited-state intramolecular proton transfer reacts without a barrier between E and K or E* and K*. The energy gap between the first excited electronic state S{sub 1} 1({pi}, {pi}*){sup 1} and the second excited electronic state S{sub 2} 2(n, {pi}*){sup 1} of E is only 0.019 eV at CIS/6-31G** level. So the S{sub 0} {yields} S{sub 1} and S{sub 0} {yields} S{sub 2} excitation may occur at the same time, and the S{sub 1} state may occur the EISPT process and result a large Stokes shifted fluorescence. And the S{sub 2} state may through internal conversion to the S{sub 1} state or intersystem crossing to the T{sub 2} state. These theoretical results contrast with the conclusion of Nakayama and his coworkers [M. Hagiri, N. Ichinose, J. Kinugasa, T. Iwasa, T. Nakayama, Chem. Lett. 33 (2004) 326] stating the present of two ground-state conformers of HBP.

  2. Evolutionary Dynamics of Pandemic Methicillin-Sensitive Staphylococcus aureus ST398 and Its International Spread via Routes of Human Migration

    Science.gov (United States)

    McAdam, Paul R.; Sullivan, Sean B.; Knox, Justin R.; Khiabanian, Hossein; Rabadan, Raul; Davies, Peter R.; Fitzgerald, J. Ross; Lowy, Franklin D.

    2017-01-01

    ABSTRACT Methicillin-susceptible Staphylococcus aureus (MSSA) accounts for the majority of S. aureus infections globally, and yet surprisingly little is known about its clonal evolution. We applied comparative whole-genome sequencing (WGS) analyses to epidemiologically and geographically diverse ST398-MSSA, a pandemic lineage affecting both humans and livestock. Bayesian phylogenetic analysis predicted divergence of human-associated ST398-MSSA ~40 years ago. Isolates from Midwestern pigs and veterinarians differed substantially from those in New York City (NYC). Pig ST398 strains contained a large region of recombination representing imports from multiple sequence types (STs). Phylogeographic analyses supported the spread of ST398-MSSA along local cultural and migratory links between parts of the Caribbean, North America, and France, respectively. Applying pairwise single-nucleotide polymorphism (SNP) distances as a measure of genetic relatedness between isolates, we observed that ST398 not only clustered in households but also frequently extended across local social networks. Isolates collected from environmental surfaces reflected the full diversity of colonizing individuals, highlighting their potentially critical role as reservoirs for transmission and diversification. Strikingly, we observed high within-host SNP variability compared to our previous studies on the dominant methicillin-resistant Staphylococcus aureus (MRSA) clone USA300. Our data indicate that the dynamics of colonization, persistence, and transmission differ substantially between USA300-MRSA and ST398-MSSA. Taken together, our study reveals local and international routes of transmission for a major MSSA clone, indicating key impacts of recombination and mutation on genetic diversification and highlighting important ecological differences from epidemic USA300. Our study demonstrates extensive local and international routes of transmission for a major MSSA clone despite the lack of substantial

  3. Intramolecular Hydrogen Bond in Biologically Active o-Carbonyl Hydroquinones

    Directory of Open Access Journals (Sweden)

    Maximiliano Martínez-Cifuentes

    2014-07-01

    Full Text Available Intramolecular hydrogen bonds (IHBs play a central role in the molecular structure, chemical reactivity and interactions of biologically active molecules. Here, we study the IHBs of seven related o-carbonyl hydroquinones and one structurally-related aromatic lactone, some of which have shown anticancer and antioxidant activity. Experimental NMR data were correlated with theoretical calculations at the DFT and ab initio levels. Natural bond orbital (NBO and molecular electrostatic potential (MEP calculations were used to study the electronic characteristics of these IHB. As expected, our results show that NBO calculations are better than MEP to describe the strength of the IHBs. NBO energies (∆Eij(2 show that the main contributions to energy stabilization correspond to LPàσ* interactions for IHBs, O1…O2-H2 and the delocalization LPàπ* for O2-C2 = Cα(β. For the O1…O2-H2 interaction, the values of ∆Eij(2 can be attributed to the difference in the overlap ability between orbitals i and j (Fij, instead of the energy difference between them. The large energy for the LP O2àπ* C2 = Cα(β interaction in the compounds 9-Hydroxy-5-oxo-4,8, 8-trimethyl-l,9(8H-anthracenecarbolactone (VIII and 9,10-dihydroxy-4,4-dimethylanthracen-1(4H-one (VII (55.49 and 60.70 kcal/mol, respectively when compared with the remaining molecules (all less than 50 kcal/mol, suggests that the IHBs in VIII and VII are strongly resonance assisted.

  4. Nonlinear dynamic singularity analysis of two interconnected synchronous generator system with 1:3 internal resonance and parametric principal resonance

    Institute of Scientific and Technical Information of China (English)

    Xiaodong WANG; Yushu CHEN; Lei HOU

    2015-01-01

    The bifurcation analysis of a simple electric power system involving two synchronous generators connected by a transmission network to an infinite-bus is carried out in this paper. In this system, the infinite-bus voltage are considered to maintain two fluctuations in the amplitude and phase angle. The case of 1:3 internal resonance between the two modes in the presence of parametric principal resonance is considered and examined. The method of multiple scales is used to obtain the bifurcation equations of this system. Then, by employing the singularity method, the transition sets determining different bifurcation patterns of the system are obtained and analyzed, which reveal the effects of the infinite-bus voltage amplitude and phase fluctuations on bifurcation patterns of this system. Finally, the bifurcation patterns are all examined by bifurcation diagrams. The results obtained in this paper will contribute to a better understanding of the complex nonlinear dynamic behaviors in a two-machine infinite-bus (TMIB) power system.

  5. 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.

  6. The interplay of skeletal deformations and ultrafast excited-state intramolecular proton transfer: Experimental and theoretical investigation of 10-hydroxybenzo[h]quinoline

    Energy Technology Data Exchange (ETDEWEB)

    Schriever, Christian [Fakultaet fuer Physik - Ludwig-Maximilians-Universitaet (LMU), Oettingenstrasse 67, 80538 Muenchen (Germany)], E-mail: christian.schriever@physik.uni-muenchen.de; Barbatti, Mario [Institute for Theoretical Chemistry - University of Vienna, Waehringer Strasse 17, 1090 Vienna (Austria)], E-mail: mario.barbatti@univie.ac.at; Stock, Kai [Fakultaet fuer Physik - Ludwig-Maximilians-Universitaet (LMU), Oettingenstrasse 67, 80538 Muenchen (Germany); Aquino, Adelia J.A.; Tunega, Daniel [Institute for Theoretical Chemistry - University of Vienna, Waehringer Strasse 17, 1090 Vienna (Austria); Lochbrunner, Stefan [Fakultaet fuer Physik - Ludwig-Maximilians-Universitaet (LMU), Oettingenstrasse 67, 80538 Muenchen (Germany); Riedle, Eberhard [Fakultaet fuer Physik - Ludwig-Maximilians-Universitaet (LMU), Oettingenstrasse 67, 80538 Muenchen (Germany)], E-mail: eberhard.riedle@physik.uni-muenchen.de; Vivie-Riedle, Regina de [Department Chemie - Ludwig-Maximilians-Universitaet (LMU), Butenandt-Strasse 11, 81377 Muenchen (Germany)], E-mail: regina.de_vivie@cup.uni-muenchen.de; Lischka, Hans [Institute for Theoretical Chemistry - University of Vienna, Waehringer Strasse 17, 1090 Vienna (Austria)], E-mail: hans.lischka@univie.ac.at

    2008-05-23

    The excited-state intramolecular proton transfer in the aromatic polycycle 10-hydroxybenzo[h]quinoline is investigated by means of transient absorption experiments with 30 fs time resolution, classical dynamics and wavepacket dynamics. The experiments establish the ultrafast transfer after UV excitation and show signatures of coherent vibrational motion in the keto product. To elucidate details of the proton transfer mechanism, the classical dynamics is also performed for 2-(2'-hydroxyphenyl)benzothiazole and the results are compared. For both systems the proton transfer takes place on the ultrafast scale of 30-40 fs, with good agreement between the theoretical investigations and the measurements. The dynamics simulations show that for both molecules the proton is handed over by means of skeletal deformation of the molecule. Due to the more rigid structure of 10-hydroxybenzo[h]quinoline the hydrogen migration mode participates more actively than in 2-(2'-hydroxyphenyl)benzothiazole.

  7. Intramolecular Torque, an Indicator of the Internal Rotation Direction of Rotor Molecules and Similar Systems

    CERN Document Server

    Zhang, Rui-Qin; Qi, Fei; Hermann, Klaus; Van Hove, Michel A

    2016-01-01

    Torque is ubiquitous in many molecular systems, including collisions, chemical reactions, vibrations, electronic excitations and especially rotor molecules. We present a straightforward theoretical method based on forces acting on atoms and obtained from atomistic quantum mechanics calculations, to quickly and qualitatively determine whether a molecule or sub-unit thereof has a tendency to rotation and, if so, around which axis and in which sense: clockwise or counterclockwise. The method also indicates which atoms, if any, are predominant in causing the rotation. Our computational approach can in general efficiently provide insights into the rotational ability of many molecules and help to theoretically screen or modify them in advance of experiments or before analyzing their rotational behavior in more detail with more extensive computations guided by the results from the torque approach. As an example, we demonstrate the effectiveness of the approach using a specific light-driven molecular rotary motor whi...

  8. FPGA implementation of a modified FitzHugh-Nagumo neuron based causal neural network for compact internal representation of dynamic environments

    Science.gov (United States)

    Salas-Paracuellos, L.; Alba, Luis; Villacorta-Atienza, Jose A.; Makarov, Valeri A.

    2011-05-01

    Animals for surviving have developed cognitive abilities allowing them an abstract representation of the environment. This internal representation (IR) may contain a huge amount of information concerning the evolution and interactions of the animal and its surroundings. The temporal information is needed for IRs of dynamic environments and is one of the most subtle points in its implementation as the information needed to generate the IR may eventually increase dramatically. Some recent studies have proposed the compaction of the spatiotemporal information into only space, leading to a stable structure suitable to be the base for complex cognitive processes in what has been called Compact Internal Representation (CIR). The Compact Internal Representation is especially suited to be implemented in autonomous robots as it provides global strategies for the interaction with real environments. This paper describes an FPGA implementation of a Causal Neural Network based on a modified FitzHugh-Nagumo neuron to generate a Compact Internal Representation of dynamic environments for roving robots, developed under the framework of SPARK and SPARK II European project, to avoid dynamic and static obstacles.

  9. 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.

  10. Dynamics and internal structure of an Alaskan debris-covered glacier from repeat airborne photogrammetry and surface geophysics

    Science.gov (United States)

    Holt, John; Levy, Joseph; Petersen, Eric; Larsen, Chris; Fahnestock, Mark

    2016-04-01

    Debris-covered glaciers and rock glaciers encompass a range of compositions and activity, and can be useful paleoclimate indicators. They also respond differently to ongoing climate change than glaciers without a protective cover. Their flow dynamics are not well understood, and their unique surface morphologies, including lobate fronts and arcuate ridges, likely result from viscous flow influenced by a combination of composition, structure, and climatic factors. However, basic connections between flow kinematics and surface morphology have not yet been established, limiting our ability to understand these features. In order to begin to address this problem we have undertaken airborne and surface studies of multiple debris-covered glaciers in Alaska and the western U.S. Sourdough Rock Glacier in the St. Elias Mountains, Alaska, is completely debris-covered and exhibits numerous transverse compressional ridges. Its trunk also exhibits highly regular bumps and swales with a wavelength of ~175 m and amplitudes up to 12 m. In the middle trunk, lineations (boulder trains and furrows) bend around a point roughly 200m from the eastern edge. We acquired five high-resolution airborne surveys of Sourdough Rock Glacier between late 2013 and late 2015 using lidar and photogrammetry to assess annual and seasonal change at the sub-meter level. Differencing the DTMs provides vertical change while feature tracking in orthophotos provide horizontal velocities that indicate meters of annual motion. The flow field is highly correlated with surface features; in particular, compressional ridges in the lower lobe. Stranded, formerly active lobes are also apparent. Surface geophysical studies were undertaken to constrain internal structure and composition using a combination of ground-penetrating radar (GPR) at 50 and 100 MHz in six transects, and time-domain electromagnetic (TDEM) measurements at 47 locations, primarily in an along-flow transect and two cross-flow transects. We infer

  11. Dynamic Characteristics of Transmission System for the Internal Grinder%内圆磨床传动系统的动力特性分析

    Institute of Scientific and Technical Information of China (English)

    伍建国; 孙庆鸿; 毛海军; 郁文凯; 蔡英

    2002-01-01

    基于Riccati传递矩阵法建立了内圆磨床传动系统的动力学模型.由模态柔度和弹性分布率的计算,分析了原内圆磨床传动系统的动态特性,应用动柔度与模态柔度的关系,找出传动系统的危险模态及其该模态上的薄弱环节,提出了结构修改方案,避免了参数调整的盲目性,并预测了其动态性能,在内圆磨床传动系统设计中得到了有效的应用.%The dynamics model of the transmission system of the internal grinder is established on the bases of Riccati transfer matrix. The dynamic characteristics of the internal grinder are obtained by analyzing the relationship between dynamic modal flexibility and modal flexibility, which is used to find out the dangerous model of the transmission system and its weak areas. Then design parameters of weak areas are modified, the new one from the old structure is put forward, and the dynamic characteristics of new structure are forecast through the calculations of the modal flexibility and elasticity distribution rate. This method is applied successfully in designing the transmission system of the internal grinder.

  12. The structural basis of androgen receptor activation: Intramolecular and intermolecular amino–carboxy interactions

    Science.gov (United States)

    Schaufele, Fred; Carbonell, Xavier; Guerbadot, Martin; Borngraeber, Sabine; Chapman, Mark S.; Ma, Aye Aye K.; Miner, Jeffrey N.; Diamond, Marc I.

    2005-01-01

    Nuclear receptors (NRs) are ligand-regulated transcription factors important in human physiology and disease. In certain NRs, including the androgen receptor (AR), ligand binding to the carboxy-terminal domain (LBD) regulates transcriptional activation functions in the LBD and amino-terminal domain (NTD). The basis for NTD–LBD communication is unknown but may involve NTD–LBD interactions either within a single receptor or between different members of an AR dimer. Here, measurement of FRET between fluorophores attached to the NTD and LBD of the AR established that agonist binding initiated an intramolecular NTD–LBD interaction in the nucleus and cytoplasm. This intramolecular folding was followed by AR self-association, which occurred preferentially in the nucleus. Rapid, ligand-induced intramolecular folding and delayed association also were observed for estrogen receptor-α but not for peroxisome proliferator activated receptor-γ2. An antagonist ligand, hydroxyflutamide, blocked the NTD–LBD association within AR. NTD–LBD association also closely correlated with the transcriptional activation by heterologous ligands of AR mutants isolated from hormone-refractory prostate tumors. Intramolecular folding, but not AR–AR affinity, was disrupted by mutation of an α-helical (23FQNLF27) motif in the AR NTD previously described to interact with the AR LBD in vitro. This work establishes an intramolecular NTD–LBD conformational change as an initial component of ligand-regulated NR function. PMID:15994236

  13. 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 Ma and Mb with distinct activation energies Eact,a > Eact,b, the activation energies of Ma and Mb in series are nearly the same as Eact,a while those in parallel are nearly the same as Eact,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.

  14. Internal tides and sediment dynamics in the deep sea—Evidence from radioactive 234Th/ 238U disequilibria

    Science.gov (United States)

    Turnewitsch, Robert; Reyss, Jean-Louis; Nycander, Jonas; Waniek, Joanna J.; Lampitt, Richard S.

    2008-12-01

    Residual flow, barotropic tides and internal (baroclinic) tides interact in a number of ways with kilometer-scale seafloor topography such as abyssal hills and seamounts. 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 234Th relative to its conservative (non-particle-reactive) and very long-lived parent nuclide 238U. The sampling sites were downstream of, or surrounded by, fields of short seamounts and, therefore, very likely to be influenced by nearby flow/topography interactions. At the sampling sites between about 200 and 1000 m above the seafloor recurrent 'fossil' disequilibria were detected. 'Fossil' disequilibria are defined by clearly detectable 234Th/ 238U disequilibria (total 234Th radioactivity current velocities of the predominating tidal M 2 constituent: on (near-)critical seamount slopes baroclinic tides lead to localized [˜ O(1 km)] increases of the overall tidal current velocity by a factor of ˜ 2, thereby pushing the total current velocity well above the threshold for sediment erosion. The results of this and a previous study [Turnewitsch, R., Reyss, J.-L., Chapman, D.C., Thomson, J., Lampitt, R.S., 2004. Evidence for a sedimentary fingerprint of an asymmetric flow field surrounding a short seamount. Earth and Planetary Science Letters 222(3-4), 1023-1036] show that kilometer-scale flow/topography interactions leave a marine geochemical imprint. This imprint may help develop new sediment proxies for the reconstruction of past changes of fluid dynamics in the deep sea, including residual and tidal flow

  15. Dynamic fe Model of Sitting Man Adjustable to Body Height, Body Mass and Posture Used for Calculating Internal Forces in the Lumbar Vertebral Disks

    Science.gov (United States)

    Pankoke, S.; Buck, B.; Woelfel, H. P.

    1998-08-01

    Long-term whole-body vibrations can cause degeneration of the lumbar spine. Therefore existing degeneration has to be assessed as well as industrial working places to prevent further damage. Hence, the mechanical stress in the lumbar spine—especially in the three lower vertebrae—has to be known. This stress can be expressed as internal forces. These internal forces cannot be evaluated experimentally, because force transducers cannot be implementated in the force lines because of ethical reasons. Thus it is necessary to calculate the internal forces with a dynamic mathematical model of sitting man.A two dimensional dynamic Finite Element model of sitting man is presented which allows calculation of these unknown internal forces. The model is based on an anatomic representation of the lower lumbar spine (L3-L5). This lumber spine model is incorporated into a dynamic model of the upper torso with neck, head and arms as well as a model of the body caudal to the lumbar spine with pelvis and legs. Additionally a simple dynamic representation of the viscera is used. All these parts are modelled as rigid bodies connected by linear stiffnesses. Energy dissipation is modelled by assigning modal damping ratio to the calculated undamped eigenvalues. Geometry and inertial properties of the model are determined according to human anatomy. Stiffnesses of the spine model are derived from static in-vitro experiments in references [1] and [2]. Remaining stiffness parameters and parameters for energy dissipation are determined by using parameter identification to fit measurements in reference [3]. The model, which is available in 3 different postures, allows one to adjust its parameters for body height and body mass to the values of the person for which internal forces have to be calculated.

  16. 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.

  17. 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.

  18. Mean-Field Theory of Intra-Molecular Charge Ordering in (TTM--TTP)I3

    Science.gov (United States)

    Omori, Yukiko; Tsuchiizu, Masahisa; Suzumura, Yoshikazu

    2011-02-01

    We examine an intra-molecular charge-ordered (ICO) state in the multi-orbital molecular compound (TTM--TTP)I3 on the basis of an effective two-orbital model derived from ab initio calculations. Representing the model in terms of the fragment molecular-orbital (MO) picture, the ICO state is described as the charge disproportionation on the left and right fragment MOs. By applying the mean-field theory, the phase diagram of the ground state is obtained as a function of the inter-molecular Coulomb repulsion and the intra-molecular transfer integral. The ICO state is stabilized by large inter-fragment Coulomb interactions, and the small intra-molecular transfer energy between two fragment MOs. Furthermore, we examine the finite-temperature phase diagram. The relevance to the experimental observations in the molecular compound of (TTM--TTP)I3 is also discussed.

  19. The effects of intramolecular and intermolecular coordination on (31)P nuclear shielding: phosphorylated azoles.

    Science.gov (United States)

    Chernyshev, Kirill A; Larina, Ludmila I; Chirkina, Elena A; Krivdin, Leonid B

    2012-02-01

    The effects of intramolecular and intermolecular coordination on (31)P nuclear shielding have been investigated in the series of tetracoordinated, pentacoordinated and hexacoordinated N-vinylpyrazoles and intermolecular complexes of N-vinylimidazole and 1-allyl-3,5-dimethylpyrazole with phosphorous pentachloride both experimentally and theoretically. It was shown that either intramolecular or intermolecular coordination involving phosphorous results in a dramatic (31)P nuclear shielding amounting to approximately 150 ppm on changing the phosphorous coordination number by one. A major importance of solvent effects on (31)P nuclear shielding of intramolecular and intermolecular complexes involving N → P coordination bond has been demonstrated. It was found that the zeroth-order regular approximation-gauge-including atomic orbital-B1PW91/DZP method was sufficiently accurate for the calculation of (31)P NMR chemical shifts, provided relativistic corrections are taken into account, the latter being of crucial importance in the description of (31)P nuclear shielding.

  20. The dynamics of "stretched molecules": Experimental studies of highly vibrationally excited molecules with stimulated emission pumping

    NARCIS (Netherlands)

    Silva, M.; Jongma, R.; Field, R. W.; Wodtke, A. M.

    2001-01-01

    We review stimulated emission pumping as used to study molecular dynamics. The review presents unimolecular as well as scattering studies. Topics include intramolecular vibrational redistribution, unimolecular isomerization and dissociation, van der Waals clusters, rotational energy transfer, vibrat

  1. Structure and dynamics of cationic van-der-Waals clusters. II. Dynamics of protonated argon clusters

    Science.gov (United States)

    Ritschel, T.; Zuhrt, Ch.; Zülicke, L.; Kuntz, P. J.

    2007-01-01

    A diatomics-in-molecules (DIM) model with ab-initio input data, which in part I successfully described the structure and bonding properties of protonated argon clusters ArnH+, is used here to investigate some aspects of the dynamics of such aggregates for n up to 30. The simple triatomic ionic fragment, Ar2H+, is studied in some detail with respect to normal vibrations, characteristics of classical intramolecular dynamics as reflected in the Fourier spectra of dynamical variables, and accurate quantum states of the vibrational motion. For larger clusters ArnH+ (n ≤30), the normal vibrational frequencies (and displacement eigenvectors) are calculated and related to the cluster structure. In addition, the Fourier spectra are analyzed with respect to their variation with changing internal energy and cluster size. As expected, the clusters show some floppy character. Even a little vibrational excitation can lead to internal rearrangement and to Ar-atom evaporation from the clusters; this is studied in more detail for one small complex (n = 3). Electronic excitation to one of the low-lying excited states, which are all globally repulsive, leads to complete fragmentation (atomization) of the clusters. A variety of conceivable elementary collision processes involving protonated argon clusters are discussed. Some of these may play a role in the gas-phase formation of medium-sized ArnH+ aggregates.

  2. 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...

  3. Large molecules on surfaces: deposition and intramolecular STM manipulation by directional forces

    Science.gov (United States)

    Grill, Leonhard

    2010-03-01

    Intramolecular manipulation of single molecules on a surface with a scanning tunnelling microscope enables the controlled modification of their structure and, consequently, their physical and chemical properties. This review presents examples of intramolecular manipulation experiments with rather large molecules, driven by directional, i.e. chemical or electrostatic, forces between tip and molecule. It is shown how various regimes of forces can be explored and characterized with one and the same manipulation of a single molecule by changing the tip-surface distance. Furthermore, different deposition techniques under ultrahigh vacuum conditions are discussed because the increasing functionality of such molecules can lead to fragmentation during the heating step, making their clean deposition difficult.

  4. The effect of intramolecular quantum modes on free energy relationships for electron transfer reactions

    DEFF Research Database (Denmark)

    Ulstrup, Jens; Jortner, Joshua

    1975-01-01

    -frequency intramolecular degrees of feedom on the free energy relationship for series of closely related reactions was investigated for various model systems involving displacement of potential energy surfaces, frequency shift, and anharmonicity effects. The free energy plots are generally found to pass through a maximum...... and to be asymmetric with a slower decrease in the transition probability with increasing energy of reaction. For high-frequency intramolecular modes this provides a rationalization of the experimental observation of ''activationless'' regions. Isotope effects are discussed as also are the oscillatory free energy...

  5. 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.

  6. 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 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 differences

  7. Comparison of path integral molecular dynamics methods for the infrared absorption spectrum of liquid water

    Science.gov (United States)

    Habershon, Scott; Fanourgakis, George S.; Manolopoulos, David E.

    2008-08-01

    The ring polymer molecular dynamics (RPMD) and partially adiabatic centroid molecular dynamics (PA-CMD) methods are compared and contrasted in an application to the infrared absorption spectrum of a recently parametrized flexible, polarizable, Thole-type potential energy model for liquid water. Both methods predict very similar spectra in the low-frequency librational and intramolecular bending region at wavenumbers below 2500 cm-1. However, the RPMD spectrum is contaminated in the high-frequency O-H stretching region by contributions from the internal vibrational modes of the ring polymer. This problem is avoided in the PA-CMD method, which adjusts the elements of the Parrinello-Rahman mass matrix so as to shift the frequencies of these vibrational modes beyond the spectral range of interest. PA-CMD does not require any more computational effort than RPMD and it is clearly the better of the two methods for simulating vibrational spectra.

  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...

  9. Asymmetric synthesis of N,O-heterocycles via enantioselective iridium-catalysed intramolecular allylic amidation

    NARCIS (Netherlands)

    Zhao, Depeng; Fananas-Mastral, Martin; Chang, Mu-Chieh; Otten, Edwin; Feringa, Ben L.

    2014-01-01

    Chiral N,O-heterocycles were synthesized in high yields and excellent enantioselectivity up to 97% ee via iridium-catalysed intramolecular allylic substitution with nucleophilic attack by the amide oxygen atom. The resulting benzoxazine derivatives were further transformed into challenging chiral

  10. Homoallylic amines by reductive inter- and intramolecular coupling of allenes and nitriles

    Directory of Open Access Journals (Sweden)

    Marija D. Manojlovic

    2011-06-01

    Full Text Available The one-pot hydrozirconation of allenes and nitriles followed by an in situ transmetalation of the allylzirconocene with dimethylzinc or zinc chloride provides functionalized homoallylic amines. An intramolecular version of this process leads to 3-aminotetrahydrofurans and 3-aminotetrahydropyrans.

  11. New amidines from intramolecular cyclization in triflic acid of nitroketene aminals with a tethered phenyl ring

    Indian Academy of Sciences (India)

    Soro Yaya; Bamba Fanté; Siaka Sorho; Coustard Jean-Marie; Adima A Augustin

    2007-05-01

    Nitroketene aminals with a tethered phenyl group underwent an intramolecular cyclization in trifluoromethanesulfonic acid to afford the corresponding N-(3-ethyl-hydrohydroxyiminobenzocycloalkenylidene) methylamine trifluoromethanesulfonate. The yields were fair to good excepted for the starting compound 1-[N-ethyl-N-(2-phenylethyl)amino]-1-methylamino-2-nitroethene.

  12. Total synthesis of (+/-)-cytisine via the intramolecular heck cyclization of activated N-alkyl glutarimides.

    Science.gov (United States)

    Coe, J W

    2000-12-28

    [reaction:see text] A synthesis of racemic cytisine 1 has been developed utilizing an intramolecular Heck cyclization to prepare the bridged tricyclic intermediate 2. The cyclization employs activated glutarimide-derived ketene aminals 3 (X = P(O)OEt(2) or SO(2)CF(3)) and represents the first use of such intermediates in metal-catalyzed processes.

  13. 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 str

  14. A new class of rhodium complexes containing free donor atoms and their intramolecular substitution reaction

    Institute of Scientific and Technical Information of China (English)

    JIANG, Hua; YUAN, Guo-Qing; ZHANG, Shu-Feng; PAN, Ping-Lai; DIAO, Kai-Sheng

    2000-01-01

    A new class of rhodium complexes with high catalytic activity as well as excellent stability, which was used as catalyst for carlbonylation of methanol to acetic acid, is reported. It con tains free donor (namely un-coordinated donor) atoms which enable to improve its stability by intramolecular substitution rearction. Its synthesis, characteristic and catalytic reaction were discussed here.

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

    KAUST Repository

    Whited, Matthew T.

    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.

  16. Resonance fluorescence as a probe to elucidate mechanisms of intramolecular relaxation processes

    Energy Technology Data Exchange (ETDEWEB)

    Chen, K.; Yeung, E.S.

    1979-12-15

    Density matrix formalism is used to study resonance fluorescence processes of isolated gaseous molecules. The Wangsness--Bloch--Fano theory is applied to the irreversible intramolecular relaxation process. In the present treatment, it is assumed that the rotational angular momentum J is a constant of motion in the zeroth order approximation. Thus intramolecular interactions can be classified as tensor operators with respect to J. The fluorescence decay patterns depend on excitation bandwidths and monitoring conditions. Under narrow band excitation, the population (monopole), orientation (dipole), and alignment (quadrupole) of the excited state density matrix rho/sub e/ can be prepared. For a sharply prepared angular momentum state under pulsed excitation, the population does not undergo radiationless decay and the resonance fluorescence intensity is a sum of three exponentials in general. For cw experiments, where lifetime limited linewidth or polarized fluorescence intensities are measured, the population can decay via an intramolecular relaxation channel providing the orientation component is initially prepared. Explicit J dependences of lifetimes are given for pulsed experiments. Under broad band excitation, quantum beats due to the coherence of rho/sub e/ are derived from the Liouville equation. Most important of all, the population can decay under pulsed, broad-band excitation conditions. The scalar part of the nonadiabatic coupling becomes an additional contributor to the intramolecular relaxation process in this last case.

  17. 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...

  18. 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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Hsu, C.-H. [Lab. Pharm. Biopharm., Department of Biotechnology, Yuanpei University, Hsin Chu, Taiwan (China); Lin, S.-Y. [Lab. Pharm. Biopharm., Department of Biotechnology, Yuanpei University, Hsin Chu, Taiwan (China)], E-mail: sylin@mail.ypu.edu.tw

    2009-03-20

    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{sup -1} for water liberated and at 1701 cm{sup -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.

  20. 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

    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...

  1. Intramolecular and Lattice Melting in n-Alkane Monolayers: An Analog of Melting in Lipid Bilayers

    DEFF Research Database (Denmark)

    Hansen, Flemming Yssing; Herwig, K.W.; Matthies, B.

    1999-01-01

    to 350 K above which a large thermal expansion and decrease in coherence length occurs. The MD simulations provide evidence that this behavior is due to a phase transition in the monolayer in which intramolecular and translational order are lost simultaneously. This melting transition is qualitatively...

  2. Intra-molecular cohesion of coils mediated by phenylalanine-glycine motifs in the natively unfolded domain of a nucleoporin

    Energy Technology Data Exchange (ETDEWEB)

    Krishnan, V V; Lau, E Y; Yamada, J; Denning, D P; Patel, S S; Colvin, M E; Rexach, M F

    2007-04-19

    The nuclear pore complex (NPC) provides the sole aqueous conduit for macromolecular exchange between the nucleus and cytoplasm of cells. Its conduit contains a size-selective gate and is populated by a family of NPC proteins that feature long natively-unfolded domains with phenylalanine-glycine repeats. These FG nucleoporins play key roles in establishing the NPC permeability barrier, but little is known about their dynamic structure. Here we used molecular modeling and biophysical techniques to characterize the dynamic ensemble of structures of a representative FG domain from the yeast nucleoporin Nup116. The results show that its FG motifs function as intra-molecular cohesion elements that impart order to the FG domain. The cohesion of coils mediated by FG motifs in the natively unfolded domain of Nup116 supports a type of tertiary structure, a native pre-molten globule, that could become quaternary at the NPC through recruitment of neighboring FG nucleoporins, forming one cohesive meshwork of intertwined filaments capable of gating protein diffusion across the NPC by size exclusion.

  3. The actin-microtubule cross-linking activity of Drosophila Short stop is regulated by intramolecular inhibition.

    Science.gov (United States)

    Applewhite, Derek A; Grode, Kyle D; Duncan, Mara C; Rogers, Stephen L

    2013-09-01

    Actin and microtubule dynamics must be precisely coordinated during cell migration, mitosis, and morphogenesis--much of this coordination is mediated by proteins that physically bridge the two cytoskeletal networks. We have investigated the regulation of the Drosophila actin-microtubule cross-linker Short stop (Shot), a member of the spectraplakin family. Our data suggest that Shot's cytoskeletal cross-linking activity is regulated by an intramolecular inhibitory mechanism. In its inactive conformation, Shot adopts a "closed" conformation through interactions between its NH(2)-terminal actin-binding domain and COOH-terminal EF-hand-GAS2 domain. This inactive conformation is targeted to the growing microtubule plus end by EB1. On activation, Shot binds along the microtubule through its COOH-terminal GAS2 domain and binds to actin with its NH(2)-terminal tandem CH domains. We propose that this mechanism allows Shot to rapidly cross-link dynamic microtubules in response to localized activating signals at the cell cortex.

  4. Competing Intramolecular vs. Intermolecular Hydrogen Bonds in Solution

    OpenAIRE

    Nagy, Peter I.

    2014-01-01

    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 in...

  5. Competing Intramolecular vs. Intermolecular Hydrogen Bonds in Solution

    OpenAIRE

    Nagy, Peter I.

    2014-01-01

    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 int...

  6. Aromatic ring strain in arylselenenyl bromides: role in facile synthesis of selenenate esters via intramolecular cyclization.

    Science.gov (United States)

    Selvakumar, K; Singh, Harkesh B; Butcher, Ray J

    2010-09-10

    The synthesis and reactivity of 2,6-disubstituted arylselenium compounds derived from 2-bromo-5-tert-butylisophthalic acid (43) are described. The syntheses of bis(5-tert-butylisophthalic acid dimethyl ester)diselenide (46) and bis(5-tert-butylisophthalic acid diisopropyl ester)diselenide (47) have been achieved by the reaction of the corresponding ester precursors with disodium diselenide. Reduction of diselenide 46 with lithium aluminum hydride affords 2,2'-bis(5-tert-butylbenzene-1,3-dimethanol)diselenide (53). Diselenides 46 and 47 exhibit intramolecular Se...O interaction. Compound 53 does not show any intramolecular Se...O interaction. The anomalous Se...O nonbonded coordination observed in the single-crystal X-ray structures of compounds 46, 47 and 53 is compared and contrasted. The corresponding selenenyl bromides 54 and 55, derived from the reaction of diselenides 46 and 47 with bromine, are quite stable in the solid state. However, they undergo hydrolysis and subsequent intramolecular cyclization upon heating or after having been kept in solution over a period of time to give the corresponding selenenate esters 56 and 57. The X-ray crystallographic study and density functional theory calculations on 54 at the B3LYP/6-31G(d) level of theory indicate a significant distortion in planarity of the aromatic ring. Glutathione peroxidase-like activities of diselenides 46 and 47 and their selenenate esters 56 and 57 have been studied both by thiophenol and bioassay methods. The very low glutathione peroxidase-like activity of the diselenides (46 and 47) and their selenenate esters (56 and 57) in the thiophenol assay is attributed to the presence of the relatively strong Se...O intramolecular interaction in the selenenyl sulfide intermediates. The interaction retards the catalytic activity through both thiol exchange and an intramolecular cyclization reaction.

  7. 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....

  8. 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.

  9. Synthesis, spectral behaviour and photophysics of donor-acceptor kind of chalcones: Excited state intramolecular charge transfer and fluorescence quenching studies

    Science.gov (United States)

    Pannipara, Mehboobali; Asiri, Abdullah M.; Alamry, Khalid A.; Arshad, Muhammad N.; El-Daly, Samy A.

    2015-02-01

    The spectral and photophysical properties of two chalcones containing electron donating and accepting groups with intramolecular charge transfer characteristics were synthesized and characterized by 1H NMR, 13C NMR and X-ray crystallography. Both compounds show very strong solvent polarity dependent changes in their photophysical characteristics, namely, remarkable red shift in the emission spectra with increasing solvent polarity, large change in Stokes shift, significant reduction in the fluorescence quantum yield; indicating that the fluorescence states of these compounds are of intramolecular charge transfer (ICT) character. The solvent effect on the photophysical parameters such as singlet absorption, molar absorptivity, oscillator strength, dipole moment, fluorescence spectra, and fluorescence quantum yield of both compounds have been investigated comprehensively. For both dyes, Lippert-Mataga and Reichardt's correlations were used to estimate the difference between the excited and ground state dipole moments (Δμ). The interactions of dyes with colloidal silver nanoparticles (Ag NPs) were also studied in ethanol using steady state fluorescence quenching measurements. The fluorescence quenching data reveal that dynamic quenching and energy transfer play a major role in the fluorescence quenching of dyes by Ag NPs.

  10. 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)

  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. Quantitative Measurement of Longitudinal and Transverse Cross-Relaxation Rates: An Application to the Analysis of the Internal Dynamics of Ranalexin in Water and Trifluoroethanol

    Science.gov (United States)

    Malliavin, T. E.; Desvaux, H.; Aumelas, A.; Chavanieu, A.; Delsuc, M. A.

    1999-09-01

    We describe a quantitative processing method which gives access to the longitudinal and transverse cross-relaxation rates from off-resonance ROESY intensities. This method takes advantage of the dependence of the off-resonance ROESY experiments at any mixing time and any spin-lock angle θ on two relaxation matrices, the longitudinal and the transverse ones. This allows one to take into account multistep magnetization transfers even if the measurements are performed only at one or two mixing times. The ratio of the longitudinal to transverse cross-relaxation rates can then be used as a local indicator of the internal dynamics, without assuming a structure or a model of motion. After validation of this processing method by numerical simulations, it is applied to the analysis of the dynamics of the peptide ranalexin dissolved in pure water and in water/TFE.

  13. 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.

  14. Gas-phase intramolecular elimination reaction studies of steviol glycosides in positive electrospray and tandem mass spectrometry.

    Science.gov (United States)

    Upreti, Mani; Clos, John F; Somayajula, Kasi V; Milanowski, Dennis J; Mocek, Ulla; Dubois, Grant E; Prakash, Indra

    2009-01-01

    This paper reports the first study of the gas-phase intramolecular elimination reaction of steviol glycosides in positive electrospray mass spectrometry. The observed glycosylated product ions are proposed to be formed via an intramolecular elimination of sugar units from the parent molecule ion. It was further proven by MS/MS studies and deuterium labeling experiments with one of the steviol glycosides, rebaudioside A. These mass spectrometric results confirmed that the new glycosylated product ions observed are most likely formed by the combination of glucose moieties (Glu) II-IV and Glu I via a gas-phase intramolecular elimination reaction.

  15. Identification of two tyrosine residues required for the intramolecular mechanism implicated in GIT1 activation.

    Directory of Open Access Journals (Sweden)

    Antonio Totaro

    Full Text Available GIT1 is an ArfGAP and scaffolding protein regulating cell adhesion and migration. The multidomain structure of GIT1 allows the interaction with several partners. Binding of GIT1 to some of its partners requires activation of the GIT1 polypeptide. Our previous studies indicated that binding of paxillin to GIT1 is enhanced by release of an intramolecular interaction between the amino-terminal and carboxy-terminal portions that keeps the protein in a binding-incompetent state. Here we have addressed the mechanism mediating this intramolecular inhibitory mechanism by testing the effects of the mutation of several formerly identified GIT1 phosphorylation sites on the binding to paxillin. We have identified two tyrosines at positions 246 and 293 of the human GIT1 polypeptide that are needed to keep the protein in the inactive conformation. Interestingly, mutation of these residues to phenylalanine did not affect binding to paxillin, while mutation to either alanine or glutamic acid enhanced binding to paxillin, without affecting the constitutive binding to the Rac/Cdc42 exchange factor βPIX. The involvement of the two tyrosine residues in the intramolecular interaction was supported by reconstitution experiments showing that these residues are important for the binding between the amino-terminal fragment and carboxy-terminal portions of GIT1. Either GIT1 or GIT1-N tyrosine phosphorylation by Src and pervanadate treatment to inhibit protein tyrosine phosphatases did not affect the intramolecular binding between the amino- and carboxy-terminal fragments, nor the binding of GIT1 to paxillin. Mutations increasing the binding of GIT1 to paxillin positively affected cell motility, measured both by transwell migration and wound healing assays. Altogether these results show that tyrosines 246 and 293 of GIT1 are required for the intramolecular inhibitory mechanism that prevents the binding of GIT1 to paxillin. The data also suggest that tyrosine

  16. Economic Development and the Market Place for Education: Dynamics of the International Schools Sector in Shanghai, China

    Science.gov (United States)

    Yamato, Yoko; Bray, Mark

    2006-01-01

    To some extent, all schools operate in a market place; but the interaction with the market place may be particularly evident in the international schools sector, since many such schools are operated by foundations or private companies which charge fees. This article focuses on the distinctive market place of Shanghai, China, which has undergone…

  17. Desorption Dynamics, Internal Energies and Imaging of Organic Molecules from Surfaces with Laser Desorption and Vacuum Ultraviolet (VUV) Photoionization

    Energy Technology Data Exchange (ETDEWEB)

    Kostko, Oleg; Takahashi, Lynelle K.; Ahmed, Musahid

    2011-04-05

    There is enormous interest in visualizing the chemical composition of organic material that comprises our world. A convenient method to obtain molecular information with high spatial resolution is imaging mass spectrometry. However, the internal energy deposited within molecules upon transfer to the gas phase from a surface can lead to increased fragmentation and to complications in analysis of mass spectra. Here it is shown that in laser desorption with postionization by tunable vacuum ultraviolet (VUV) radiation, the internal energy gained during laser desorption leads to minimal fragmentation of DNA bases. The internal temperature of laser-desorbed triacontane molecules approaches 670 K, whereas the internal temperature of thymine is 800 K. A synchrotron-based VUV postionization technique for determining translational temperatures reveals that biomolecules have translational temperatures in the range of 216-346 K. The observed low translational temperatures, as well as their decrease with increased desorption laser power is explained by collisional cooling. An example of imaging mass spectrometry on an organic polymer, using laser desorption VUV postionization shows 5 mu m feature details while using a 30 mu m laser spot size and 7 ns duration. Applications of laser desorption postionization to the analysis of cellulose, lignin and humic acids are briefly discussed.

  18. Dynamics of clinical semiotics in children with pathological tortuosity of internal carotid arteries in remote period after surgical management.

    Science.gov (United States)

    Shoĭkhet, Ya N; Khorev, N G; Kulikova, N I; Beller, A V; Kulikov, V P; Miller, V E

    2010-01-01

    The present study enrolling a total of eighty-eight 4-to-16-year-old children and adolescents was aimed at detailed elaboration and formalization of clinical signs of the internal carotid artery pathological kinking syndrome. To achieve these objectives, the authors carried out a comparative analysis of clinical manifestations of the disease in the surgically treated subjects (constituting the Surgery Group comprising 43 children and adolescents) and non-operated patients (making up the Comparison Group consisting of 45 age- and gender-matched subjects). There were no baseline differences in the incidence rate of clinical syndromes and symptoms between the groups of the would-be operated and conservatively treated patients. Also studied were the remote outcomes (1-to-12-year follow up) of surgical correction for pathological tortuosity of the internal carotid artery. The incidence rate of regression of neurological symptomatology along different clinical signs after surgery was shown to vary within a wide range from 11.6% to 96.3%. Resection of the proximal portion of the internal carotid artery with re-implantation into the old ostium turned out to be clinically effective in 90.0% of cases, with the haemodynamic efficacy amounting to 83.3%. Arteriolysis of the internal carotid artery rendered a clinical effect in 75% of cases, with a haemodynamical effect thereof equalling 25.0%. The decision as to the type of a surgical intervention to perform was primarily made based on the findings of angiography of the internal carotid artery. The operation of arteriolysis did not lead to deterioration of the child's condition.

  19. Highly efficient light-emitting diodes based on intramolecular rotation

    CERN Document Server

    Di, Dawei; Yang, Le; Jones, Saul; Friend, Richard H; Linnolahti, Mikko; Bochmann, Manfred; Credgington, Dan

    2016-01-01

    The efficiency of an organic light-emitting diode (OLED) is fundamentally governed by the spin of recombining electron-hole pairs (singlet and triplet excitons), since triplets cannot usually emit light. The singlet-triplet energy gap, a key factor for efficient utilization of triplets, is normally positive. Here we show that in a family of materials with amide donor and carbene acceptor moieties linked by a metal, this energy gap for singlet and triplet excitons with charge-transfer character can be tuned from positive to negative values via the rotation of donor and acceptor about the metal-amide bond. When the gap is close to zero, facile intersystem crossing is possible, enabling efficient emission from singlet excitons. We demonstrate solution-processed LEDs with exceptionally high quantum efficiencies (near-100% internal and >27% external quantum efficiencies), and current and power efficiencies (87 cd/A and 75 lm/W) comparable to, or exceeding, those of state-of-the-art vacuum-processed OLEDs and quant...

  20. 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.

  1. Molecular Dynamics Studies of Energy Transfer Processes in Crystal Systems.

    Science.gov (United States)

    1984-11-30

    Computer molecular dynamics studies have been carried out on the problem of attaining a fundamental understanding of shock-induced initiation of...intramolecular energy exchange in shock-loaded systems are presented. Originator-supplied keywords include: Molecular dynamics , Energy transfer, Shock front, Shock wave, Explosives, Shock structure.

  2. Enantioselective Intramolecular Hydroarylation of Alkenes via Directed C-H Bond Activation

    Energy Technology Data Exchange (ETDEWEB)

    Harada, Hitoshi; Thalji, Reema; Bergman, Robert; Ellman, Jonathan

    2008-05-22

    Highly enantioselective catalytic intramolecular ortho-alkylation of aromatic imines containing alkenyl groups tethered at the meta position relative to the imine directing group has been achieved using [RhCl(coe){sub 2}]{sub 2} and chiral phosphoramidite ligands. Cyclization of substrates containing 1,1- and 1,2-disubstituted as well as trisubstituted alkenes were achieved with enantioselectivities >90% ee for each substrate class. Cyclization of substrates with Z-alkene isomers proceeded much more efficiently than substrates with E-alkene isomers. This further enabled the highly stereoselective intramolecular alkylation of certain substrates containing Z/E-alkene mixtures via a Rh-catalyzed alkene isomerization with preferential cyclization of the Z-isomer.

  3. Isotope effects on chemical shifts in the study of intramolecular hydrogen bonds

    DEFF Research Database (Denmark)

    Hansen, Poul Erik

    2015-01-01

    The paper deals with the use of isotope effects on chemical shifts in characterizing intramolecular hydrogen bonds. Both so-called resonance-assisted (RAHB) and non-RAHB systems are treated. The importance of RAHB will be discussed. Another very important issue is the borderline between “static......” and tautomeric systems. Isotope effects on chemical shifts are particularly useful in such studies. All kinds of intramolecular hydrogen bonded systems will be treated, typical hydrogen bond donors: OH, NH, SH and NH+, typical acceptors C=O, C=N, C=S C=N−. The paper will be deal with both secondary and primary...... isotope effects on chemical shifts. These two types of isotope effects monitor the same hydrogen bond, but from different angles...

  4. Rapid Synthesis of Size-controlled Gold Nanoparticles by Complex Intramolecular Photoreduction

    Institute of Scientific and Technical Information of China (English)

    DONG Shou-an; YANG Sheng-chun; TANG Chun

    2007-01-01

    A rapid synthesis of size-controlled gold nanoparticles was proposed. The method is based on the sensitive intramolecular photoreduction reaction of Fe( Ⅲ )-EDTA complex in chloroacetic acid-sodium acetate buffer solution,where Fe(Ⅱ)-EDTA complex generated by photo-promotion acts as a reductant of AuCl4- ions. Gold nanoparticles formed were stabilized by EDTA ligand or other protective agents added. As a result, well-dispersed gold nanoparticles with an average diameter range of 6.7 to 50. 9 nm were obtained. According to the characterizations by the UV spectrum and TEM, the intramolecular charge transfer of the excited states of complex Fe(Ⅲ) -EDTA and the mechanism of forming gold nanoparticles were discussed in detail.

  5. Intramolecular hydrogen bonds in crystals of thiophosphorylbenzopyrane derivatives X-ray and FT-IR studies

    Science.gov (United States)

    Rybarczyk-Pirek, Agnieszka J.; Dubis, Alina T.; Grabowski, Sławomir J.; Nawrot-Modranka, Jolanta

    2006-01-01

    The crystal structures of two new benzopyrane derivatives are analyzed and compared with previous X-ray investigations on related compounds. A particular attention is focused on intramolecular interactions. For the chromone derivatives ( 1 and 3) only one kind of interaction is possible, i.e., N-H⋯O, whereas for the coumarine derivatives ( 2 and 4) two types of intramolecular hydrogen bonding are observed - N-H⋯O and O-H⋯N. Two types of H-bond for coumarine derivatives are the result of the existence of two tautomeric forms - enamine and iminoenol. Combined spectroscopic, NMR and IR measurements confirm such tautomeric equilibrium in solution. The influence of the additional intermolecular hydrogen bonds on the stabilization of tautomeric forms in crystals is also discussed here.

  6. Computational study of topological effects on intramolecular electron transfer in mixed-valence compounds

    Institute of Scientific and Technical Information of China (English)

    Yinxi YU; Haobin WANG

    2011-01-01

    The constrained density functional theory (CDFT) was used to investigate the topological effects on intramolecular electron transfer processes that have been reported in previous experimental work [Inorg.Chem.,1997,36 (22),pp 5037-50491.The computation mainly focused on three isomers of diferrocenylbenzenes (ortho,para,and meta) and 5-substituted derivatives of m-diferrocencylbenzenes with R =NH2,Cl,CH3,CN,NO2,N(CH3)3+3,and N+2.The influence of a third group R' (R' =NH2 and N+2) was introduced to the ortho and para isomers.The calculations were compared with the experimental results.The relation between the substituted functional groups and the effectiveness of intramolecular electron transfer was discussed on the basis of CDFT computational results.

  7. Enantioselective Intramolecular Hydroarylation of Alkenes via Directed C-H Bond Activation

    Energy Technology Data Exchange (ETDEWEB)

    Harada, Hitoshi; Thalji, Reema; Bergman, Robert; Ellman, Jonathan

    2008-05-22

    Highly enantioselective catalytic intramolecular ortho-alkylation of aromatic imines containing alkenyl groups tethered at the meta position relative to the imine directing group has been achieved using [RhCl(coe){sub 2}]{sub 2} and chiral phosphoramidite ligands. Cyclization of substrates containing 1,1- and 1,2-disubstituted as well as trisubstituted alkenes were achieved with enantioselectivities >90% ee for each substrate class. Cyclization of substrates with Z-alkene isomers proceeded much more efficiently than substrates with E-alkene isomers. This further enabled the highly stereoselective intramolecular alkylation of certain substrates containing Z/E-alkene mixtures via a Rh-catalyzed alkene isomerization with preferential cyclization of the Z-isomer.

  8. 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.

  9. [Analyses of biogenic related compounds based on intramolecular excimer-forming fluorescence derivatization].

    Science.gov (United States)

    Yoshida, Hideyuki

    2003-08-01

    A highly selective and sensitive method based on a novel concept is introduced for the assay of biological substances. This method is based on an intramolecular excimer-forming fluorescence derivatization with a pyrene reagent, followed by reverse-phase HPLC. Polyamines, polyphenols, and dicarboxylic acids, which have two or more reactive functional groups in a molecule, were converted to the corresponding polypyrene-labeled derivatives by reaction with the appropriate pyrene reagent. The derivatives exhibited intramolecular excimer fluorescence (440-520 nm), which can clearly be discriminated from the monomer (normal) fluorescence (360-420 nm) emitted by pyrene reagents and monopyrene-labeled derivatives of monofunctional compounds. With excimer fluorescence detection, highly selective and sensitive determination of polyamines, polyphenols, and dicarboxylic acids can be achieved. Furthermore, the methods were successfully applied to the determination of various biological and environmental substances in real samples, which require only a small amount of sample and simple pretreatment.

  10. 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.

  11. A Chiral Thiourea as a Template for Enantioselective Intramolecular [2 + 2] Photocycloaddition Reactions

    Science.gov (United States)

    2016-01-01

    A chiral (1R,2R)-diaminocyclohexane-derived bisthiourea was found to exhibit a significant asymmetric induction in the intramolecular [2 + 2] photocycloaddition of 2,3-dihydropyridone-5-carboxylates. Under optimized conditions, the reaction was performed with visible light employing 10 mol % of thioxanthone as triplet sensitizer. Due to the different electronic properties of its carbonyl oxygen atoms, a directed binding of the substrate to the template is possible, which in turn enables an efficient enantioface differentiation. PMID:27258626

  12. 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...

  13. 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.

  14. 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.

  15. Intramolecular azide to alkene cycloadditions for the construction of pyrrolobenzodiazepines and azetidino-benzodiazepines.

    Science.gov (United States)

    Hemming, Karl; Chambers, Christopher S; Jamshaid, Faisal; O'Gorman, Paul A

    2014-10-17

    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.

  16. 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.

  17. Photoinduced Intramolecular Cyclopentanation vs Photoprotolytic Oxametathesis in Polycyclic Alkenes Outfitted with Conformationally Constrained Aroylmethyl Chromophores‡

    OpenAIRE

    Valiulin, Roman A.; Arisco, Teresa M.; Kutateladze, Andrei G.

    2012-01-01

    Intramolecular photoinduced cyclizations are investigated in photoprecursors assembled in a modular fashion via a Diels-Alder reaction of acetylenic dienophiles with subsequent Michael additions of aromatic ketones to install a chromophore capable of initiating Paternò-Büchi cycloadditions or radical cyclization cascades. The protolytic oxametathesis in these systems allows for rapid access to novel polycyclic scaffolds decorated by formyl groups and carboxylates suitable for subsequent modif...

  18. Intramolecular tautomerisation and the conformational variability of some classical mutagens – cytosine derivatives: quantum chemical study

    OpenAIRE

    Hovorun D. M.; Brovarets’ O. O.

    2011-01-01

    Aim. To determine the lifetime of the mutagenic cytosine derivatives through the investigation of the physicochemical mechanisms of their intramolecular proton transfer. Methods. Non-empirical quantum chemistry, the analysis of the electron density by means of Bader’s atoms in molecules (AIM) theory and physicochemical kinetics were used. Results. It is shown that the modification of all investigated compounds, except DCyt, prevents their pairing in both mutagenic and canonical tautomeric for...

  19. Copper-catalysed intramolecular O-arylation: a simple and efficient method for benzoxazole synthesis.

    Science.gov (United States)

    Wu, Fengtian; Zhang, Jie; Wei, Qianbing; Liu, Ping; Xie, Jianwei; Jiang, Haojie; Dai, Bin

    2014-12-21

    A wide range of 2-substituted benzoxazoles can be efficiently synthesized from N-(2-iodo-/bromo-phenyl)benzamides, and even the less reactive N-(2-chlorophenyl)benzamides, via Cu-catalysed intramolecular coupling cyclization reactions using methyl 2-methoxybenzoate as the ligand under mild reaction conditions. In addition, the benzoxazoles can be easily prepared from the primary amides coupling with o-dihalobenzenes in a single step.

  20. Addition of boranes to N-aryl-salicylaldimines: intramolecular hydrogenation of imines.

    Science.gov (United States)

    Barnes, Stephanie S; Vogels, Christopher M; Decken, Andreas; Westcott, Stephen A

    2011-05-07

    Addition of boranes to N-aryl-salicylaldimines takes place initially at the reactive phenolic O-H bond to give an activated boron-containing imine and dihydrogen. In some cases a subsequent intramolecular hydrogenation step is observed and the C=N imine bond is reduced to the corresponding amine. Reactions with dimesitylborane in THF are unique in that the reduced amine product is the major product observed in solution.