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Sample records for complex exciton-phonon coupling

  1. Optical properties of MgZnO alloys: Excitons and exciton-phonon complexes

    SciTech Connect

    Neumann, M. D.; Cobet, C.; Esser, N.; Laumer, B.; Wassner, T. A.; Eickhoff, M.; Feneberg, M.; Goldhahn, R.

    2011-07-01

    The characteristics of the excitonic absorption and emission around the fundamental bandgap of wurtzite Mg{sub x}Zn{sub 1-x}O grown on c-plane sapphire substrates by plasma assisted molecular beam epitaxy with Mg contents between x = 0 and x = 0.23 are studied using spectroscopic ellipsometry and photoluminescence (PL) measurements. The ellipsometric data were analyzed using a multilayer model yielding the dielectric function (DF). The imaginary part of the DF for the alloys exhibits a pronounced feature which is attributed to exciton-phonon coupling (EPC) similar to the previously reported results for ZnO. Thus, in order to determine reliable transition energies, the spectral dependence is analyzed by a model which includes free excitonic lines, the exciton continuum, and the enhanced absorption due to EPC. A line shape analysis of the temperature-dependent PL spectra yielded in particular the emission-related free excitonic transition energies, which are compared to the results from the DF line-shape analysis. The PL linewidth is discussed within the framework of an alloy disorder model.

  2. Communication: Exciton-phonon information flow in the energy transfer process of photosynthetic complexes

    SciTech Connect

    Rebentrost, P.; Aspuru-Guzik, Alan

    2011-03-14

    Non-Markovian and nonequilibrium phonon effects are believed to be key ingredients in the energy transfer in photosynthetic complexes, especially in complexes which exhibit a regime of intermediate exciton–phonon coupling. In this work, we utilize a recently developed measure for non-Markovianity to elucidate the exciton–phonon dynamics in terms of the information flow between electronic and vibrational degrees of freedom. We study the measure in the hierarchical equation of motion approach which captures strong coupling effects and nonequilibrium molecular reorganization. We propose an additional trace distance measure for the information flow that could be extended to other master equations. We find that for a model dimer system and for the Fenna–Matthews–Olson complex the non-Markovianity is significant under physiological conditions.

  3. Surface strain engineering through Tb doping to study the pressure dependence of exciton-phonon coupling in ZnO nanoparticles

    SciTech Connect

    Sharma, A.; Dhar, S. Singh, B. P.; Nayak, C.; Bhattacharyya, D.; Jha, S. N.

    2013-12-07

    A compressive hydrostatic strain has been found to develop in the ZnO lattice as a result of accumulation of Tb ions on the surface of the nanoparticles for Tb mole-fraction less than 0.04. This hydrostatic strain can be controlled up to ≈14 GPa by varying the Tb mole-fraction. Here, we have utilized this novel technique of surface strain engineering through Tb doping for introducing hydrostatic compressive strain in the lattice to study the pressure dependent electronic and vibrational properties of ZnO nanoparticles. Our study reveals that when subjected to pressure, nanoparticles of ZnO behave quite differently than bulk in many aspects. Unlike bulk ZnO, which is reported to go through a wurtzite to rock-salt structural phase transition at ≈8 GPa, ZnO nanoparticles do not show such transition and remain in wurtzite phase even at 14 GPa of pressure. Furthermore, the Grüneisen parameters for the optical phonon modes are found to be order of magnitude smaller in ZnO nanoparticles as compared to bulk. Our study also suggests an increase of the dielectric constant with pressure, which is opposite to what has been reported for bulk ZnO. Interestingly, it has also been found that the exciton-phonon interaction depends strongly upon pressure in this system. The exciton-phonon coupling has been found to decrease as pressure increases. A variational technique has been adopted to theoretically calculate the exciton-LO phonon coupling coefficient in ZnO nanoparticles as a function of pressure, which shows a good agreement with the experimental results. These findings imply that surface engineering of ZnO nanoparticles with Tb could indeed be an efficient tool to enhance and control the optical performance of this material.

  4. Low Exciton-Phonon Coupling, High Charge Carrier Mobilities, and Multiexciton Properties in Two-Dimensional Lead, Silver, Cadmium, and Copper Chalcogenide Nanostructures.

    PubMed

    Ding, Yuchen; Singh, Vivek; Goodman, Samuel M; Nagpal, Prashant

    2014-12-18

    The development of two-dimensional (2D) nanomaterials has revealed novel physical properties, like high carrier mobilities and the tunable coupling of charge carriers with phonons, which can enable wide-ranging applications in optoelectronic and thermoelectric devices. While mechanical exfoliation of graphene and some transition metal dichalcogenides (e.g., MoS2, WSe2) has enabled their fabrication as 2D semiconductors and integration into devices, lack of similar syntheses for other 2D semiconductor materials has hindered further progress. Here, we report measurements of fundamental charge carrier interactions and optoelectronic properties of 2D nanomaterials made from two-monolayers-thick PbX, CdX, Cu2X, and Ag2X (X = S, Se) using colloidal syntheses. Extremely low coupling of charge carriers with phonons (2-6-fold lower than bulk and other low-dimensional semiconductors), high carrier mobilities (0.2-1.2 cm(2) V(-1) s(-1), without dielectric screening), observation of infrared surface plasmons in ultrathin 2D semiconductor nanostructures, strong quantum-confinement, and other multiexcitonic properties (different phonon coupling and photon-to-charge collection efficiencies for band-edge and higher-energy excitons) can pave the way for efficient solution-processed devices made from these 2D nanostructured semiconductors. PMID:26273976

  5. Atypical Exciton-Phonon Interactions in WS2 and WSe2 Monolayers Revealed by Resonance Raman Spectroscopy.

    PubMed

    Del Corro, E; Botello-Méndez, A; Gillet, Y; Elias, A L; Terrones, H; Feng, S; Fantini, C; Rhodes, Daniel; Pradhan, N; Balicas, L; Gonze, X; Charlier, J-C; Terrones, M; Pimenta, M A

    2016-04-13

    Resonant Raman spectroscopy is a powerful tool for providing information about excitons and exciton-phonon coupling in two-dimensional materials. We present here resonant Raman experiments of single-layered WS2 and WSe2 using more than 25 laser lines. The Raman excitation profiles of both materials show unexpected differences. All Raman features of WS2 monolayers are enhanced by the first-optical excitations (with an asymmetric response for the spin-orbit related XA and XB excitons), whereas Raman bands of WSe2 are not enhanced at XA/B energies. Such an intriguing phenomenon is addressed by DFT calculations and by solving the Bethe-Salpeter equation. These two materials are very similar. They prefer the same crystal arrangement, and their electronic structure is akin, with comparable spin-orbit coupling. However, we reveal that WS2 and WSe2 exhibit quite different exciton-phonon interactions. In this sense, we demonstrate that the interaction between XC and XA excitons with phonons explains the different Raman responses of WS2 and WSe2, and the absence of Raman enhancement for the WSe2 modes at XA/B energies. These results reveal unusual exciton-phonon interactions and open new avenues for understanding the two-dimensional materials physics, where weak interactions play a key role coupling different degrees of freedom (spin, optic, and electronic). PMID:26998817

  6. Energy transfer in finite-size exciton-phonon systems: Confinement-enhanced quantum decoherence

    NASA Astrophysics Data System (ADS)

    Pouthier, Vincent

    2012-09-01

    Based on the operatorial formulation of the perturbation theory, the exciton-phonon problem is revisited for investigating exciton-mediated energy flow in a finite-size lattice. Within this method, the exciton-phonon entanglement is taken into account through a dual dressing mechanism so that exciton and phonons are treated on an equal footing. In a marked contrast with what happens in an infinite lattice, it is shown that the dynamics of the exciton density is governed by several time scales. The density evolves coherently in the short-time limit, whereas a relaxation mechanism occurs over intermediated time scales. Consequently, in the long-time limit, the density converges toward a nearly uniform distributed equilibrium distribution. Such a behavior results from quantum decoherence that originates in the fact that the phonons evolve differently depending on the path followed by the exciton to tunnel along the lattice. Although the relaxation rate increases with the temperature and with the coupling, it decreases with the lattice size, suggesting that the decoherence is inherent to the confinement.

  7. Observations of exciton-surface plasmon polariton coupling and exciton-phonon coupling in InGaN/GaN quantum wells covered with Au, Ag, and Al films

    NASA Astrophysics Data System (ADS)

    Estrin, Y.; Rich, D. H.; Keller, S.; DenBaars, S. P.

    2015-07-01

    The coupling of excitons to surface plasmon polaritons (SPPs) and longitudinal optical (LO) phonons in Au-, Ag-, and Al-coated InxGa1-xN/GaN multiple and single quantum wells (SQWs) was studied with time-resolved cathodoluminescence (CL) and CL wavelength imaging techniques. Excitons were generated in the metal-coated SQWs by injecting a pulsed high-energy electron beam through the thin metal films, which is found to be an ideal method of excitation for plasmonic quantum heterostructures and nanostructures which are opaque to laser/light excitation. The Purcell enhancement factor (Fp) at low temperatures was obtained by the direct measurement of changes in the carrier lifetime caused by the SQW excitonSPP coupling. The deposition of thin films of Al, Ag, and Au on an InGaN/GaN QW enabled a comparison of excitonSPP coupling for energy ranges in which the surface plasmon energy is greater than, approximately equal to, and less than the QW excitonic transition energy. We investigated the temperature dependence of the Huang-Rhys factors for exciton-to-LO phonon coupling for the metal-covered and bare samples. CL imaging and spectroscopy with variable excitation densities are used to examine the spatial correlations between CL emission intensity, carrier lifetime, QW excitonic emission energy, and the Huang-Rhys factor, all of which are strongly influenced by local fluctuations in the In composition and formation of InN-rich centers.

  8. Observations of exciton-surface plasmon polariton coupling and exciton-phonon coupling in InGaN/GaN quantum wells covered with Au, Ag, and Al films.

    PubMed

    Estrin, Y; Rich, D H; Keller, S; DenBaars, S P

    2015-07-01

    The coupling of excitons to surface plasmon polaritons (SPPs) and longitudinal optical (LO) phonons in Au-, Ag-, and Al-coated InxGa1-xN/GaN multiple and single quantum wells (SQWs) was studied with time-resolved cathodoluminescence (CL) and CL wavelength imaging techniques. Excitons were generated in the metal-coated SQWs by injecting a pulsed high-energy electron beam through the thin metal films, which is found to be an ideal method of excitation for plasmonic quantum heterostructures and nanostructures which are opaque to laser/light excitation. The Purcell enhancement factor (Fp) at low temperatures was obtained by the direct measurement of changes in the carrier lifetime caused by the SQW exciton-SPP coupling. The deposition of thin films of Al, Ag, and Au on an InGaN/GaN QW enabled a comparison of exciton-SPP coupling for energy ranges in which the surface plasmon energy is greater than, approximately equal to, and less than the QW excitonic transition energy. We investigated the temperature dependence of the Huang-Rhys factors for exciton-to-LO phonon coupling for the metal-covered and bare samples. CL imaging and spectroscopy with variable excitation densities are used to examine the spatial correlations between CL emission intensity, carrier lifetime, QW excitonic emission energy, and the Huang-Rhys factor, all of which are strongly influenced by local fluctuations in the In composition and formation of InN-rich centers. PMID:26076324

  9. Exciton-phonon system on a star graph: A perturbative approach

    NASA Astrophysics Data System (ADS)

    Yalouz, Saad; Pouthier, Vincent

    2016-05-01

    Based on the operatorial formulation of the perturbation theory, the properties of an exciton coupled with optical phonons on a star graph are investigated. Within this method, the dynamics is governed by an effective Hamiltonian, which accounts for exciton-phonon entanglement. The exciton is dressed by a virtual phonon cloud whereas the phonons are clothed by virtual excitonic transitions. In spite of the coupling with the phonons, it is shown that the energy spectrum of the dressed exciton resembles that of a bare exciton. The only differences originate in a polaronic mechanism that favors an energy shift and a decay of the exciton hopping constant. By contrast, the motion of the exciton allows the phonons to propagate over the graph so that the dressed normal modes drastically differ from the localized modes associated to bare phonons. They define extended vibrations whose properties depend on the state occupied by the exciton that accompanies the phonons. It is shown that the phonon frequencies, either red shifted or blue shifted, are very sensitive to the model parameter in general, and to the size of the graph in particular.

  10. Influence of Effects of Self-Polarization and Exciton-Phonon Interactions on the Exciton Energy in Lead Iodide Nanofilms

    NASA Astrophysics Data System (ADS)

    Kramar, V. M.; Pugantseva, O. V.

    2014-08-01

    In the approximation of effective masses for electronic and phononic - dielectric continuum - systems, the influence of spatial bounding, self-polarization, and exciton-phonon interactions on the exciton state in a flat double nanoheterostructure (a nanofilm) - lead iodide in a polymer matrix -is theoretically investigated for the model of a single infinitely deep quantum well. It is demonstrated that the dominating factor determining the energy of the bottom of the ground exciton band and its binding energy is spatial bounding. The relationship between two other effects depends on the nanofilm thickness, namely, the influence of the self-polarization effect in ultrathin films significantly exceeds that of exciton-phonon interaction.

  11. Theory of femtosecond coherent double-pump single-molecule spectroscopy: Application to light harvesting complexes

    SciTech Connect

    Chen, Lipeng; Zhao, Yang; Gelin, Maxim F.; Domcke, Wolfgang

    2015-04-28

    We develop a first principles theoretical description of femtosecond double-pump single-molecule signals of molecular aggregates. We incorporate all singly excited electronic states and vibrational modes with significant exciton-phonon coupling into a system Hamiltonian and treat the ensuing system dynamics within the Davydov D{sub 1} Ansatz. The remaining intra- and inter-molecular vibrational modes are treated as a heat bath and their effect is accounted for through lineshape functions. We apply our theory to simulate single-molecule signals of the light harvesting complex II. The calculated signals exhibit pronounced oscillations of mixed electron-vibrational (vibronic) origin. Their periods decrease with decreasing exciton-phonon coupling.

  12. Energetic pulses in exciton-phonon molecular chains and conservative numerical methods for quasilinear Hamiltonian systems.

    PubMed

    Lemesurier, Brenton

    2013-09-01

    The phenomenon of coherent energetic pulse propagation in exciton-phonon molecular chains such as α-helix protein is studied using an ODE system model of Davydov-Scott type, both with numerical studies using a new unconditionally stable fourth-order accurate energy-momentum conserving time discretization and with analytical explanation of the main numerical observations. Impulsive initial data associated with initial excitation of a single amide-I vibration by the energy released by ATP hydrolysis are used as well as the best current estimates of physical parameter values. In contrast to previous studies based on a proposed long-wave approximation by the nonlinear Schrödinger (NLS) equation and focusing on initial data resembling the soliton solutions of that equation, the results here instead lead to approximation by the third derivative nonlinear Schrödinger equation, giving a far better fit to observed behavior. A good part of the behavior is indeed explained well by the linear part of that equation, the Airy PDE, while other significant features do not fit any PDE approximation but are instead explained well by a linearized analysis of the ODE system. A convenient method is described for construction of the highly stable, accurate conservative time discretizations used, with proof of its desirable properties for a large class of Hamiltonian systems, including a variety of molecular models. PMID:24125294

  13. Excitons and exciton-phonon interactions in 2D MoS2 , WS2 and WSe2 studied by resonance Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Pimenta, Marcos; Del Corro, Elena; Carvalho, Bruno; Malard, Leandro; Alves, Juliana; Fantini, Cristiano; Terrones, Humberto; Elias, Ana Laura; Terrones, Mauricio

    The 2D materials exhibit a very strong exciton binding energy, and the exciton-phonon coupling plays an important role in their optical properties. Resonance Raman spectroscopy (RRS) is a very useful tool to provide information about excitons and their couplings with phonons. We will present in this work a RRS study of different samples of 2D transition metal dichalcogenides (MoS2, WS2 and WSe2) with one, two and three layers (1L, 2L, 3L) and bulk samples, using more than 30 different laser excitation lines covering the visible range. We have observed that all Raman features are enhanced by resonances with excitonic transitions. From the laser energy dependence of the Raman excitation profile (REP) we obtained the energies of the excitonic states and their dependence with the number of atomic layers.. In the case of MoS2, we observed that the electron-phonon coupling is symmetry dependent, and our results provide experimental evidence of the C exciton recently predicted theoretically. The RRS results WSe2 show that the Raman modes are enhanced by the excited excitonic states and we will present the dependence of the excited states energies on the number of layers.

  14. Exciton-phonon interaction and Raman spectra of [(CH3)2NH2]5Cd2CuCl11 crystals

    NASA Astrophysics Data System (ADS)

    Kapustianik, V.; Batiuk, A.; Czapla, Z.; Podsiada, D.; Czupiski, O.; Eliyachevskyy, Yu.; Rudyk, V.

    2004-09-01

    Temperature evolution of the exciton-phonon interaction (EPI) in ((CH3)2NH2)5Cd2CuCl11 solid solution was studied on the basis of absorption spectroscopy data. The obtained values of effective phonon energies were compared with the data of Raman spectroscopy. It is shown that the (T) and E parameters of Urbach's rule show the continuous anomalous change characteristic of the second-order phase transition at T1 = 176 K. The anomalous behaviour of the EPI and other spectral parameters at T0 = 310-315 K was related to the complex co-operative effect involving weakening of the hydrogen bonds and variation of the Jahn-Teller distortion of metal-halogen polyhedra with temperature. This process takes place only within the copper-chlorine sublattice and due to this would be hardly related to the usual phase transition. At the same time, the considered temperature change of the tetragonal distortion of the metal-halogen octahedra is followed by nonfulfillment of Urbach's rule in the temperature range T T0.

  15. Spatial confinement, self-polarization and exciton-phonon interaction effect on the location of exciton line in lead iodide nanofilms

    NASA Astrophysics Data System (ADS)

    Kramar, V. M.; Pugantseva, O. V.; Derevyanchuk, A. V.

    2014-08-01

    Theoretical investigation of the spatial confinement, self-polarization and exciton-phonon interaction influence on the exciton state in plane double nanoheterostructure (nanofilm)-lead iodide in polymeric matrix is performed within the effective mass approximation for the electron and dielectric continuum for the phonons in the framework of infinitely deep single quantum well. It is shown that spatial confinement is the dominating feature determining the energy of the bottom of exciton ground band and its binding energy. The relationship of two others depends on nanofilm thickness: in ultrathin films the influence of self-polarization effect is essentially bigger than the role of exciton-phonon interaction.

  16. Role of exciton-phonon interactions and disordering processes in the formation of the absorption edge in Cu6P(S1- x Sex)5Br crystals

    NASA Astrophysics Data System (ADS)

    Studenyak, I. P.; Kranjcec, M.; Suslikov, L. M.; Kovacs, D. Sh.; Pan'ko, V. V.

    2002-04-01

    The absorption edge in Cu6P(S1- x Sex)5Br crystals has been studied for strong absorption in the temperature range of 77 330 K. The parameters of the Urbach absorption edge and exciton-phonon interactions in Cu6P(S1- x Sex)5Br crystals are determined and their effect on the composition disorder is studied.

  17. Parametric resonance-induced time-convolutionless master equation breakdown in finite size exciton-phonon systems.

    PubMed

    Pouthier, Vincent

    2010-09-29

    A detailed analysis is performed to show that the second order time-convolutionless master equation fails to describe the exciton-phonon dynamics in a finite size lattice. To proceed, special attention is paid to characterizing the coherences of the exciton reduced density matrix. These specific elements measure the ability of the exciton to develop superimpositions involving the vacuum and the one-exciton states. It is shown that the coherences behave as wavefunctions whose dynamics is governed by a time-dependent effective Hamiltonian defined in terms of the so-called time-dependent relaxation operator. Due to the confinement, quantum recurrences provide to the relaxation operator an almost periodic nature, so the master equation reduces to a linear system of differential equations with almost periodic coefficients. We show that, in accordance with the Floquet theory, unstable solutions emerge due to parametric resonances involving specific frequencies of the relaxation operator and specific excitonic eigenfrequencies. These resonances give rise to an unphysical exponential growth of the coherences, indicating the breakdown of the second order master equation. PMID:21386551

  18. Transport of quantum excitations coupled to spatially extended nonlinear many-body systems

    NASA Astrophysics Data System (ADS)

    Iubini, Stefano; Boada, Octavi; Omar, Yasser; Piazza, Francesco

    2015-11-01

    The role of noise in the transport properties of quantum excitations is a topic of great importance in many fields, from organic semiconductors for technological applications to light-harvesting complexes in photosynthesis. In this paper we study a semi-classical model where a tight-binding Hamiltonian is fully coupled to an underlying spatially extended nonlinear chain of atoms. We show that the transport properties of a quantum excitation are subtly modulated by (i) the specific type (local versus non-local) of exciton-phonon coupling and by (ii) nonlinear effects of the underlying lattice. We report a non-monotonic dependence of the exciton diffusion coefficient on temperature, in agreement with earlier predictions, as a direct consequence of the lattice-induced fluctuations in the hopping rates due to long-wavelength vibrational modes. A standard measure of transport efficiency confirms that both nonlinearity in the underlying lattice and off-diagonal exciton-phonon coupling promote transport efficiency at high temperatures, preventing the Zeno-like quench observed in other models lacking an explicit noise-providing dynamical system.

  19. Probing ultrafast excitation energy transfer of the chlorosome with exciton-phonon variational dynamics.

    PubMed

    Somoza Márquez, Alejandro; Chen, Lipeng; Sun, Kewei; Zhao, Yang

    2016-07-27

    The chlorosome antenna complex is a fascinating structure which due to its immense scale, accurate simulation of excitation energy transfer (EET) dynamics supposes a genuine computational challenge. Resonant vibronic modes have been recently identified in 2D spectra of the chlorosome which motivates our present endeavour of modelling electronic and vibrational degrees of freedom on an equal footing. Following the Dirac-Frenkel time-dependent variational principle, we exploit a general theory of polaron dynamics in two-dimensional lattices based on the Holstein molecular crystal model and investigate a single rod model of pigment aggregates. Unlike reduced formalisms, explicit integration of the degrees of freedom of both the system and the bath requires extensive computational resources. We exploit the architecture of graphic processor units (GPUs) by implementing our simulations on this platform. The simulation of dynamic properties of hundreds or even thousands of pigments is thus achievable in just a few hours. The potential investigation and design of natural or engineered two-dimensional pigment networks can thus be accommodated. Due to the lack of consensus regarding the precise arrangement of chromophores in the chlorosome, helicity and dimerization are investigated independently, extracting their contributions to both optical and EET properties. The presence of dimerization is found to slow down the delocalization process. Exciton delocalization is completed in 100 fs in a single rod aggregate whose dimensions (20 nm) fairly exceed the estimated extent of a coherent domain. Ultrafast energy relaxation in the exciton manifold occurs in 50 fs and the duration of super-diffusive transport is found to last for about 80 fs. PMID:26792106

  20. Coupled adaptive complex networks

    NASA Astrophysics Data System (ADS)

    Shai, S.; Dobson, S.

    2013-04-01

    Adaptive networks, which combine topological evolution of the network with dynamics on the network, are ubiquitous across disciplines. Examples include technical distribution networks such as road networks and the internet, natural and biological networks, and social science networks. These networks often interact with or depend upon other networks, resulting in coupled adaptive networks. In this paper we study susceptible-infected-susceptible (SIS) epidemic dynamics on coupled adaptive networks, where susceptible nodes are able to avoid contact with infected nodes by rewiring their intranetwork connections. However, infected nodes can pass the disease through internetwork connections, which do not change with time: The dependencies between the coupled networks remain constant. We develop an analytical formalism for these systems and validate it using extensive numerical simulation. We find that stability is increased by increasing the number of internetwork links, in the sense that the range of parameters over which both endemic and healthy states coexist (both states are reachable depending on the initial conditions) becomes smaller. Finally, we find a new stable state that does not appear in the case of a single adaptive network but only in the case of weakly coupled networks, in which the infection is endemic in one network but neither becomes endemic nor dies out in the other. Instead, it persists only at the nodes that are coupled to nodes in the other network through internetwork links. We speculate on the implications of these findings.

  1. In-situ optical transmission electron microscope study of exciton phonon replicas in ZnO nanowires by cathodoluminescence

    SciTech Connect

    Yang, Shize; Tian, Xuezeng; Wang, Lifen; Wei, Jiake; Qi, Kuo; Li, Xiaomin; Xu, Zhi E-mail: xdbai@iphy.ac.cn Wang, Wenlong; Zhao, Jimin; Bai, Xuedong E-mail: xdbai@iphy.ac.cn; Wang, Enge E-mail: xdbai@iphy.ac.cn

    2014-08-18

    The cathodoluminescence spectrum of single zinc oxide (ZnO) nanowires is measured by in-situ optical Transmission Electron Microscope. The coupling between exciton and longitudinal optical phonon is studied. The band edge emission varies for different excitation spots. This effect is attributed to the exciton propagation along the c axis of the nanowire. Contrary to free exciton emission, the phonon replicas are well confined in ZnO nanowire. They travel along the c axis and emit at the end surface. Bending strain increases the relative intensity of second order phonon replicas when excitons travel along the c-axis.

  2. Synchronization in complex dynamical networks coupled with complex chaotic system

    NASA Astrophysics Data System (ADS)

    Wei, Qiang; Xie, Cheng-Jun; Wang, Bo

    2015-11-01

    This paper investigates synchronization in complex dynamical networks with time delay and perturbation. The node of complex dynamical networks is composed of complex chaotic system. A complex feedback controller is designed to realize different component of complex state variable synchronize up to different scaling complex function when complex dynamical networks realize synchronization. The synchronization scaling function is changed from real field to complex field. Synchronization in complex dynamical networks with constant delay and time-varying coupling delay are investigated, respectively. Numerical simulations show the effectiveness of the proposed method.

  3. Unified analysis of ensemble and single-complex optical spectral data from light-harvesting complex-2 chromoproteins for gaining deeper insight into bacterial photosynthesis

    NASA Astrophysics Data System (ADS)

    Pajusalu, Mihkel; Kunz, Ralf; Rätsep, Margus; Timpmann, Kõu; Köhler, Jürgen; Freiberg, Arvi

    2015-11-01

    Bacterial light-harvesting pigment-protein complexes are very efficient at converting photons into excitons and transferring them to reaction centers, where the energy is stored in a chemical form. Optical properties of the complexes are known to change significantly in time and also vary from one complex to another; therefore, a detailed understanding of the variations on the level of single complexes and how they accumulate into effects that can be seen on the macroscopic scale is required. While experimental and theoretical methods exist to study the spectral properties of light-harvesting complexes on both individual complex and bulk ensemble levels, they have been developed largely independently of each other. To fill this gap, we simultaneously analyze experimental low-temperature single-complex and bulk ensemble optical spectra of the light-harvesting complex-2 (LH2) chromoproteins from the photosynthetic bacterium Rhodopseudomonas acidophila in order to find a unique theoretical model consistent with both experimental situations. The model, which satisfies most of the observations, combines strong exciton-phonon coupling with significant disorder, characteristic of the proteins. We establish a detailed disorder model that, in addition to containing a C2-symmetrical modulation of the site energies, distinguishes between static intercomplex and slow conformational intracomplex disorders. The model evaluations also verify that, despite best efforts, the single-LH2-complex measurements performed so far may be biased toward complexes with higher Huang-Rhys factors.

  4. Resonant energy transfer assisted by off-diagonal coupling.

    PubMed

    Wu, Ning; Sun, Ke-Wei; Chang, Zhe; Zhao, Yang

    2012-03-28

    Dynamics of resonant energy transfer of a single excitation in a molecular dimer system are studied in the simultaneous presence of diagonal and off-diagonal exciton-phonon coupling. It is found that, at given temperatures, the off-diagonal coupling can enhance both the coherence of the resonant energy transfer and the net quantity of energy transferred from an initially excited monomer to the other. Also studied is the dynamics of entanglement between the dimer system and the phonon bath as measured by the von Neumann entanglement entropy, and the inter-monomer entanglement dynamics for the excitonic system. PMID:22462880

  5. Exciton Scattering approach for conjugated macromolecules: from electronic spectra to electron-phonon coupling

    NASA Astrophysics Data System (ADS)

    Tretiak, Sergei

    2014-03-01

    The exciton scattering (ES) technique is a multiscale approach developed for efficient calculations of excited-state electronic structure and optical spectra in low-dimensional conjugated macromolecules. Within the ES method, the electronic excitations in the molecular structure are attributed to standing waves representing quantum quasi-particles (excitons), which reside on the graph. The exciton propagation on the linear segments is characterized by the exciton dispersion, whereas the exciton scattering on the branching centers is determined by the energy-dependent scattering matrices. Using these ES energetic parameters, the excitation energies are then found by solving a set of generalized ``particle in a box'' problems on the graph that represents the molecule. All parameters can be extracted from quantum-chemical computations of small molecular fragments and tabulated in the ES library for further applications. Subsequently, spectroscopic modeling for any macrostructure within considered molecular family could be performed with negligible numerical effort. The exciton scattering properties of molecular vertices can be further described by tight-binding or equivalently lattice models. The on-site energies and hopping constants are obtained from the exciton dispersion and scattering matrices. Such tight-binding model approach is particularly useful to describe the exciton-phonon coupling, energetic disorder and incoherent energy transfer in large branched conjugated molecules. Overall the ES applications accurately reproduce the optical spectra compared to the reference quantum chemistry results, and make possible to predict spectra of complex macromolecules, where conventional electronic structure calculations are unfeasible.

  6. Same-Sex Couples: Legal Complexities

    ERIC Educational Resources Information Center

    Oswald, Ramona Faith; Kuvalanka, Katherine A.

    2008-01-01

    In this article, the authors present a typology for organizing our current knowledge regarding same-sex couples in the United States who have and have not established legal ties between partners. This framework is complemented by a discussion of key rulings that define what is legally possible as well as the introduction of "legal consciousness,"…

  7. Electromagnetic coupling on complex systems - Topological approach

    NASA Astrophysics Data System (ADS)

    Parmantier, J. P.; Labaume, G.; Alliot, J. C.; Degauque, P.

    The principles of electromagnetic topology, developed by Baum, are reviewed. The method involves breaking a complex electromagnetic problem down into several small ones that are easier to solve. An example is used to illustrate the advantages of the approach.

  8. Sparse repulsive coupling enhances synchronization in complex networks.

    PubMed

    Leyva, I; Sendiña-Nadal, I; Almendral, J A; Sanjuán, M A F

    2006-11-01

    Through the last years, different strategies to enhance synchronization in complex networks have been proposed. In this work, we show that synchronization of nonidentical dynamical units that are attractively coupled in a small-world network is strongly improved by just making phase-repulsive a tiny fraction of the couplings. By a purely topological analysis that does not depend on the dynamical model, we link the emerging dynamical behavior with the structural properties of the sparsely coupled repulsive network. PMID:17279973

  9. Exciton coupling of surface complexes on a nanocrystal surface.

    PubMed

    Xu, Xiangxing; Ji, Jianwei; Wang, Guan; You, Xiaozeng

    2014-08-25

    Exciton coupling may arise when chromophores are brought into close spatial proximity. Herein the intra-nanocrystal exciton coupling of the surface complexes formed by coordination of 8-hydroxyquinoline to ZnS nanocrystals (NCs) is reported. It is studied by absorption, photoluminescence (PL), PL excitation (PLE), and PL lifetime measurements. The exciton coupling of the surface complexes tunes the PL color and broadens the absorption and PLE windows of the NCs, and thus is a potential strategy for improving the light-harvesting efficiency of NC solar cells and photocatalysts. PMID:24863364

  10. Mode-coupling instability of monolayer complex (dusty) plasmas

    NASA Astrophysics Data System (ADS)

    Zhdanov, Sergey; Ivlev, Alexei; Morfill, Gregor

    2010-05-01

    Strongly coupled complex (dusty) plasmas give us a unique opportunity to go beyond the limits of continuous media and study various generic processes occurring in liquids or solids, in regimes ranging from the onset of cooperative phenomena to large strongly coupled systems at the most detailed kinetic (atomistic) level. On the other hand, there is certain peculiarity of the interparticle interactions in complex plasmas. This can be easily understood if we divide the complete set of elementary charges in complex plasmas into two distinct categories - a subsystem of charges bound to the microparticles, and a subsystem of free plasma charges in the surrounding wakes. Plasma wakes play the role of a "third body" in the mutual particle-particle interaction and, hence, make the pair interaction nonreciprocal. We carried out rigorous theoretical investigation of the DL wave mode coupling occurring in 2D complex plasmas due to particle-wake interactions. The analysis of the mode coupling shows that if the strength of the vertical confinement is below a certain critical value, then resonance coupling between the longitudinal in-plane mode and out-of-plane mode sets in. This results in the emergence of a hybrid mode and drives the mode-coupling instability. The universal dependence of the critical confinement frequency on plasma parameters is calculated, which allows us to specify the conditions when stable 2D highly ordered complex plasma can be formed in experiments.

  11. Complex network synchronization of chaotic systems with delay coupling

    SciTech Connect

    Theesar, S. Jeeva Sathya Ratnavelu, K.

    2014-03-05

    The study of complex networks enables us to understand the collective behavior of the interconnected elements and provides vast real time applications from biology to laser dynamics. In this paper, synchronization of complex network of chaotic systems has been studied. Every identical node in the complex network is assumed to be in Lur’e system form. In particular, delayed coupling has been assumed along with identical sector bounded nonlinear systems which are interconnected over network topology.

  12. Anticipated synchronization in coupled complex Ginzburg-Landau systems.

    PubMed

    Ciszak, Marzena; Mayol, Catalina; Mirasso, Claudio R; Toral, Raul

    2015-09-01

    We study the occurrence of anticipated synchronization in two complex Ginzburg-Landau systems coupled in a master-slave configuration. Master and slave systems are ruled by the same autonomous function, but the slave system receives the injection from the master and is subject to a negative delayed self-feedback loop. We give evidence that the magnitude of the largest anticipation time, obtained for complex-valued coupling constants, depends on the dynamical regime where the system operates (defect turbulence, phase turbulence, or bichaos) and scales with the linear autocorrelation time of the system. We also provide analytical conditions for the stability of the anticipated synchronization manifold that are in qualitative agreement with those obtained numerically. Finally, we report on the existence of anticipated synchronization in coupled two-dimensional complex Ginzburg-Landau systems. PMID:26465544

  13. Anticipated synchronization in coupled complex Ginzburg-Landau systems

    NASA Astrophysics Data System (ADS)

    Ciszak, Marzena; Mayol, Catalina; Mirasso, Claudio R.; Toral, Raul

    2015-09-01

    We study the occurrence of anticipated synchronization in two complex Ginzburg-Landau systems coupled in a master-slave configuration. Master and slave systems are ruled by the same autonomous function, but the slave system receives the injection from the master and is subject to a negative delayed self-feedback loop. We give evidence that the magnitude of the largest anticipation time, obtained for complex-valued coupling constants, depends on the dynamical regime where the system operates (defect turbulence, phase turbulence, or bichaos) and scales with the linear autocorrelation time of the system. We also provide analytical conditions for the stability of the anticipated synchronization manifold that are in qualitative agreement with those obtained numerically. Finally, we report on the existence of anticipated synchronization in coupled two-dimensional complex Ginzburg-Landau systems.

  14. Distributed coupling complexity in a weakly coupled oscillatory network with associative properties

    NASA Astrophysics Data System (ADS)

    Kostorz, Kathrin; Hölzel, Robert W.; Krischer, Katharina

    2013-08-01

    We present a novel architecture of an oscillatory neural network capable of performing pattern recognition tasks. Two established strategies for obtaining associative properties in oscillatory networks invoke either a physical, time constant or a global, dynamical all-to-all coupling. Our network distributes the complexity of the coupling between the spatial and the temporal domain. Instead of {O}(N^2) physical connections or a global connection with {O}(N^2) frequency components, each of the N oscillators receives an individual coupling signal which is composed of N - 1 frequency components. We demonstrate that such a network can be built with analog electronic oscillators and possesses reliable pattern recognition properties. Theoretical analysis shows that the scalability is in fact superior to the dynamic global coupling approach, while its physical complexity is greatly reduced compared to the individual time constant coupling.

  15. Synchronization of complex networks coupled by periodically intermittent noise

    NASA Astrophysics Data System (ADS)

    Li, Shuang; Yan, Huiyun; Li, Jiaorui

    2016-04-01

    Noise is ubiquitous in real systems, so it is important to investigate the effects of noise on the network system. In this paper, the synchronization of complex network coupled by periodically intermittent noise is investigated and a sufficient condition of noise-induced synchronization is obtained analytically via stability theory of stochastic differential equation. The sufficient condition provides a theoretical reference for the analysis of the impact of coupling noise intensity, duration, coupled oscillator number and other parameters on the synchronization behavior. As examples, Rossler-like and Lorenz network systems are presented to verify the theoretical result.

  16. Magnetoelectric coupling effects in multiferroic complex oxide composite structures.

    PubMed

    Vaz, Carlos A F; Hoffman, Jason; Ahn, Charles H; Ramesh, Ramamoorthy

    2010-07-20

    The study of magnetoelectric materials has recently received renewed interest, in large part stimulated by breakthroughs in the controlled growth of complex materials and by the search for novel materials with functionalities suitable for next generation electronic devices. In this Progress Report, we present an overview of recent developments in the field, with emphasis on magnetoelectric coupling effects in complex oxide multiferroic composite materials. PMID:20414887

  17. Modeling of Emission Spectra for Molecular Rings - LH2 And LH4 Complexes

    NASA Astrophysics Data System (ADS)

    Horák, Milan; Hĕrman, Pavel; Zapletal, David

    Computer simulation of steady state fluorescence spectra of the ring molecular systems (resembling, e.g. the light harvesting rings from LH2 and LH4 photosynthetic complexes of purple bacteria) is presented in this paper. The general organization of the LH2 and LH4 complexes is the same: identical subunits are repeated cyclically in such a way that a ring-shaped structure is formed. However, the symmetries of these rings are different: LH2 is usually nonameric but LH4 is octameric. The other difference is the presence of four bacteriochlorophyll molecules per repeating unit in LH4 rather than three ones found in LH2. Transi- tion dipole moments of bacteriochlorophylls in B850 ring of LH2 have nearly tangential orientation whereas in LH4 they are organized in a more radial fashion. The dynamical aspects in ensemble of rings are reflected in optical line shapes of electronic transitions. The observed linewidths reflect the combined influence of different types of static and dynamic disorder. To avoid the broadening of lines due to ensemble averaging one uses the single-molecule spectroscopy technique to obtain a fluorescence-excitation spectrum. For our simulations we have used the ring of tightly bound two-level systems. Static disorder is taken into account simultaneously with dynamic disorder in Markovian approximation. The cumulant-expansion method of Mukamel et al. is used for the calculation of spectral responses of the system with exciton-phonon coupling. Comparison of steady state fluorescence spectra for B850 ring from LH2 and LH4 ring is done.

  18. Ultrafast Polariton-Phonon Dynamics of Strongly Coupled Quantum Dot-Nanocavity Systems

    NASA Astrophysics Data System (ADS)

    Müller, Kai; Fischer, Kevin A.; Rundquist, Armand; Dory, Constantin; Lagoudakis, Konstantinos G.; Sarmiento, Tomas; Kelaita, Yousif A.; Borish, Victoria; Vučković, Jelena

    2015-07-01

    We investigate the influence of exciton-phonon coupling on the dynamics of a strongly coupled quantum dot-photonic crystal cavity system and explore the effects of this interaction on different schemes for nonclassical light generation. By performing time-resolved measurements, we map out the detuning-dependent polariton lifetime and extract the spectrum of the polariton-to-phonon coupling with unprecedented precision. Photon-blockade experiments for different pulse-length and detuning conditions (supported by quantum optical simulations) reveal that achieving high-fidelity photon blockade requires an intricate understanding of the phonons' influence on the system dynamics. Finally, we achieve direct coherent control of the polariton states of a strongly coupled system and demonstrate that their efficient coupling to phonons can be exploited for novel concepts in high-fidelity single-photon generation.

  19. From globally coupled maps to complex-systems biology

    SciTech Connect

    Kaneko, Kunihiko

    2015-09-15

    Studies of globally coupled maps, introduced as a network of chaotic dynamics, are briefly reviewed with an emphasis on novel concepts therein, which are universal in high-dimensional dynamical systems. They include clustering of synchronized oscillations, hierarchical clustering, chimera of synchronization and desynchronization, partition complexity, prevalence of Milnor attractors, chaotic itinerancy, and collective chaos. The degrees of freedom necessary for high dimensionality are proposed to equal the number in which the combinatorial exceeds the exponential. Future analysis of high-dimensional dynamical systems with regard to complex-systems biology is briefly discussed.

  20. From globally coupled maps to complex-systems biology

    NASA Astrophysics Data System (ADS)

    Kaneko, Kunihiko

    2015-09-01

    Studies of globally coupled maps, introduced as a network of chaotic dynamics, are briefly reviewed with an emphasis on novel concepts therein, which are universal in high-dimensional dynamical systems. They include clustering of synchronized oscillations, hierarchical clustering, chimera of synchronization and desynchronization, partition complexity, prevalence of Milnor attractors, chaotic itinerancy, and collective chaos. The degrees of freedom necessary for high dimensionality are proposed to equal the number in which the combinatorial exceeds the exponential. Future analysis of high-dimensional dynamical systems with regard to complex-systems biology is briefly discussed.

  1. Structural Assembly of Molecular Complexes Based on Residual Dipolar Couplings

    PubMed Central

    Berlin, Konstantin; O’Leary, Dianne P.; Fushman, David

    2010-01-01

    We present and evaluate a rigid-body molecular docking method, called PATIDOCK, that relies solely on the three-dimensional structure of the individual components and the experimentally derived residual dipolar couplings (RDC) for the complex. We show that, given an accurate ab initio predictor of the alignment tensor from a protein structure, it is possible to accurately assemble a protein-protein complex by utilizing the RDC’s sensitivity to molecular shape to guide the docking. The proposed docking method is robust against experimental errors in the RDCs and computationally efficient. We analyze the accuracy and efficiency of this method using experimental or synthetic RDC data for several proteins, as well as synthetic data for a large variety of protein-protein complexes. We also test our method on two protein systems for which the structure of the complex and steric-alignment data are available (Lys48-linked diubiquitin and a complex of ubiquitin and a ubiquitin-associated domain) and analyze the effect of flexible unstructured tails on the outcome of docking. The results demonstrate that it is fundamentally possible to assemble a protein-protein complex based solely on experimental RDC data and the prediction of the alignment tensor from three-dimensional structures. Thus, despite the purely angular nature of residual dipolar couplings, they can be converted into intermolecular distance/translational constraints. Additionally we show a method for combining RDCs with other experimental data, such as ambiguous constraints from interface mapping, to further improve structure characterization of the protein complexes. PMID:20550109

  2. Coupled disease-behavior dynamics on complex networks: A review.

    PubMed

    Wang, Zhen; Andrews, Michael A; Wu, Zhi-Xi; Wang, Lin; Bauch, Chris T

    2015-12-01

    It is increasingly recognized that a key component of successful infection control efforts is understanding the complex, two-way interaction between disease dynamics and human behavioral and social dynamics. Human behavior such as contact precautions and social distancing clearly influence disease prevalence, but disease prevalence can in turn alter human behavior, forming a coupled, nonlinear system. Moreover, in many cases, the spatial structure of the population cannot be ignored, such that social and behavioral processes and/or transmission of infection must be represented with complex networks. Research on studying coupled disease-behavior dynamics in complex networks in particular is growing rapidly, and frequently makes use of analysis methods and concepts from statistical physics. Here, we review some of the growing literature in this area. We contrast network-based approaches to homogeneous-mixing approaches, point out how their predictions differ, and describe the rich and often surprising behavior of disease-behavior dynamics on complex networks, and compare them to processes in statistical physics. We discuss how these models can capture the dynamics that characterize many real-world scenarios, thereby suggesting ways that policy makers can better design effective prevention strategies. We also describe the growing sources of digital data that are facilitating research in this area. Finally, we suggest pitfalls which might be faced by researchers in the field, and we suggest several ways in which the field could move forward in the coming years. PMID:26211717

  3. Coupled disease-behavior dynamics on complex networks: A review

    NASA Astrophysics Data System (ADS)

    Wang, Zhen; Andrews, Michael A.; Wu, Zhi-Xi; Wang, Lin; Bauch, Chris T.

    2015-12-01

    It is increasingly recognized that a key component of successful infection control efforts is understanding the complex, two-way interaction between disease dynamics and human behavioral and social dynamics. Human behavior such as contact precautions and social distancing clearly influence disease prevalence, but disease prevalence can in turn alter human behavior, forming a coupled, nonlinear system. Moreover, in many cases, the spatial structure of the population cannot be ignored, such that social and behavioral processes and/or transmission of infection must be represented with complex networks. Research on studying coupled disease-behavior dynamics in complex networks in particular is growing rapidly, and frequently makes use of analysis methods and concepts from statistical physics. Here, we review some of the growing literature in this area. We contrast network-based approaches to homogeneous-mixing approaches, point out how their predictions differ, and describe the rich and often surprising behavior of disease-behavior dynamics on complex networks, and compare them to processes in statistical physics. We discuss how these models can capture the dynamics that characterize many real-world scenarios, thereby suggesting ways that policy makers can better design effective prevention strategies. We also describe the growing sources of digital data that are facilitating research in this area. Finally, we suggest pitfalls which might be faced by researchers in the field, and we suggest several ways in which the field could move forward in the coming years.

  4. Numerical Experiments In Strongly Coupled Complex (Dusty) Plasmas

    NASA Astrophysics Data System (ADS)

    Hou, L. J.; Ivlev A.; Hubertus M. T.; Morfill, G. E.

    2010-07-01

    Complex (dusty) plasma is a suspension of micron-sized charged dust particles in a weakly ionized plasma with electrons, ions, and neutral atoms or molecules. Therein, dust particles acquire a few thousand electron charges by absorbing surrounding electrons and ions, and consequently interact with each other via a dynamically screened Coulomb potential while undergoing Brownian motion due primarily to frequent collisions with the neutral molecules. When the interaction potential energy between charged dust particles significantly exceeds their kinetic energy, they become strongly coupled and can form ordered structures comprising liquid and solid states. Since the motion of charged dust particles in complex (dusty) plasmas can be directly observed in real time by using a video camera, such systems have been generally regarded as a promising model system to study many phenomena occurring in solids, liquids and other strongly-coupled systems at the kinetic level, such as phase transitions, transport processes, and collective dynamics. Complex plasma physics has now grown into a mature research field with a very broad range of interdisciplinary facets. In addition to usual experimental and theoretical study, computer simulation in complex plasma plays an important role in bridging experimental observations and theories and in understanding many interesting phenomena observed in laboratory. The present talk will focus on a class of computer simulations that are usually non-equilibrium ones with external perturbation and that mimic the real complex plasma experiments (i. e., numerical experiment). The simulation method, i. e., the so-called Brownian Dynamics methods, will be firstly reviewed and then examples, such as simulations of heat transfer and shock wave propagation, will be present.

  5. Coupling Through Tortuous Path Narrow Slot Apertures into Complex Cavitivies

    SciTech Connect

    Jedlicka, Russell P.; Castillo, Steven P.; Warne, Larry K.

    1999-07-26

    A hybrid FEM/MoM model has been implemented to compute the coupling of fields into a cavity through narrow slot apertures having depth. The model utilizes the slot model of Warne and Chen [23]-[29] which takes into account the depth of the slot, wall losses, and inhomogeneous dielectrics in the slot region. The cavity interior is modeled with the mixed-order, covariant-projection hexahedral elements of Crowley [32]. Results are given showing the accuracy and generality of the method for modeling geometrically complex slot-cavity combinations.

  6. Oxidative coupling of rhodium phenyl imido/amido complexes

    SciTech Connect

    Ge, Y.W.; Ye, Y.; Sharp, P.R.

    1994-09-07

    In previous work, we found that tautomeric mixtures of the late transition metal imido and amido complexes Rh{sub 2}({mu}-NPh)(CO){sub 2} ({mu}-dppm){sub 2} (1) and Rh{sub 2}({mu}-NHPh)(CO){sub 2}({mu}-dppm)({mu}-dppm-H){sup 2} (2) (hereafter designated as 1/2) undergo electrophilic ring addition reactions at the NPh group. A single electron transfer mechanism was considered. Such a mechanism would require oxidation of the imido/amido complex to a radical cation. To establish this possibility, we investigated the oxidation chemistry of this system. We found a rich chemistry consistent with formation and coupling of an amido radical cation. This chemistry, described here, is closely related to the well-studied oxidation chemistry of aniline and its derivatives. 16 refs.

  7. Emission lineshapes of the B850 band of light-harvesting 2 (LH2) complex in purple bacteria: A second order time-nonlocal quantum master equation approach

    NASA Astrophysics Data System (ADS)

    Kumar, Praveen; Jang, Seogjoo

    2013-04-01

    The emission lineshape of the B850 band in the light harvesting complex 2 of purple bacteria is calculated by extending the approach of 2nd order time-nonlocal quantum master equation [S. Jang and R. J. Silbey, J. Chem. Phys. 118, 9312 (2003), 10.1063/1.1569239]. The initial condition for the emission process corresponds to the stationary excited state density where exciton states are entangled with the bath modes in equilibrium. This exciton-bath coupling, which is not diagonal in either site excitation or exciton basis, results in a new inhomogeneous term that is absent in the expression for the absorption lineshape. Careful treatment of all the 2nd order terms are made, and explicit expressions are derived for both full 2nd order lineshape expression and the one based on secular approximation that neglects off-diagonal components in the exciton basis. Numerical results are presented for a few representative cases of disorder and temperature. Comparison of emission line shape with the absorption line shape is also made. It is shown that the inhomogeneous term coming from the entanglement of the system and bath degrees of freedom makes significant contributions to the lineshape. It is also found that the perturbative nature of the theory can result in negative portion of lineshape in some situations, which can be removed significantly by inclusion of the inhomogeneous term and completely by using the secular approximation. Comparison of the emission and absorption lineshapes at different temperatures demonstrates the role of thermal population of different exciton states and exciton-phonon couplings.

  8. Magnetic Exchange Couplings in Transition Metal Complexes from DFT

    NASA Astrophysics Data System (ADS)

    Peralta, Juan

    In this talk I will review our current efforts for the evaluation of magnetic exchange couplings in transition metal complexes from density functional theory. I will focus on the performance of different DFT approximations, including a variety of hybrid density functionals, and show that hybrid density functionals containing approximately 30% Hartree-Fock type exchange are in general among the best choice in terms of accuracy. I will also describe a novel computational method to evaluate exchange coupling parameters using analytic self-consistent linear response theory. This method avoids the explicit evaluation of energy differences, which can become impractical for large systems. Our approach is based on the evaluation of the transversal magnetic torque between two magnetic centers for a given spin configuration using explicit constraints of the local magnetization direction via Lagrange multipliers. This method is applicable in combination with any modern density functional with a noncollinear spin generalization and can be utilized as a ``black-box''. I will show proof-of-concept calculations in frustrated Fe7IIIdisk-shaped clusters, and dinuclear CuII, FeIII, and heteronuclear complexes. NSF DMR-1206920.

  9. The complex choreography of transcription-coupled repair.

    PubMed

    Spivak, Graciela; Ganesan, Ann K

    2014-07-01

    A quarter of a century has elapsed since the discovery of transcription-coupled repair (TCR), and yet our fascination with this process has not diminished. Nucleotide excision repair (NER) is a versatile pathway that removes helix-distorting DNA lesions from the genomes of organisms across the evolutionary scale, from bacteria to humans. TCR, defined as a subpathway of NER, is dedicated to the repair of lesions that, by virtue of their location on the transcribed strands of active genes, encumber elongation by RNA polymerases. In this review, we will report on newly identified proteins, protein modifications, and protein complexes that participate in TCR in Escherichia coli and in human cells. We will discuss general models for the biochemical pathways and how and when cells might choose to utilize TCR or other pathways for repair or bypass of transcription-blocking DNA alterations. PMID:24751236

  10. Proton-coupled electron transfer with photoexcited metal complexes.

    PubMed

    Wenger, Oliver S

    2013-07-16

    Proton-coupled electron transfer (PCET) plays a crucial role in many enzymatic reactions and is relevant for a variety of processes including water oxidation, nitrogen fixation, and carbon dioxide reduction. Much of the research on PCET has focused on transfers between molecules in their electronic ground states, but increasingly researchers are investigating PCET between photoexcited reactants. This Account describes recent studies of excited-state PCET with d(6) metal complexes emphasizing work performed in my laboratory. Upon photoexcitation, some complexes release an electron and a proton to benzoquinone reaction partners. Others act as combined electron-proton acceptors in the presence of phenols. As a result, we can investigate photoinduced PCET involving electron and proton transfer in a given direction, a process that resembles hydrogen-atom transfer (HAT). In other studies, the photoexcited metal complexes merely serve as electron donors or electron acceptors because the proton donating and accepting sites are located on other parts of the molecular PCET ensemble. We and others have used this multisite design to explore so-called bidirectional PCET which occurs in many enzymes. A central question in all of these studies is whether concerted proton-electron transfer (CPET) can compete kinetically with sequential electron and proton transfer steps. Short laser pulses can trigger excited-state PCET, making it possible to investigate rapid reactions. Luminescence spectroscopy is a convenient tool for monitoring PCET, but unambiguous identification of reaction products can require a combination of luminescence spectroscopy and transient absorption spectroscopy. Nevertheless, in some cases, distinguishing between PCET photoproducts and reaction products formed by simple photoinduced electron transfer (ET) (reactions that don't include proton transfer) is tricky. Some of the studies presented here deal directly with this important problem. In one case study we

  11. Exciton-phonon interaction in crystals and quantum size structures

    NASA Astrophysics Data System (ADS)

    Yaremko, A. M.; Yukhymchuk, V. O.; Dzhagan, V. M.; Valakh, M. Ya; Baran, J.; Ratajczak, H.

    2007-12-01

    In this report, the problem of electron-phonon interaction (EPI) in bulk semiconductors and quantum dots (QDs) is considered. It is shown that the model of strong EPI developed for organic molecular crystals can be successfully applied to bulk and nano-sized semiconductors. The idea of the approach proposed is to describe theoretically the experimental Raman (IR) spectra, containing the phonon replicas, by varying the EPI constant. The main parameter of the theoretical expression (βS) is the ratio of EPI constant (χS) to the frequency of the corresponding phonon mode (ΩS). The theoretical results show that variation of the QD size can change the value of χS.

  12. The use of real or complex coupling coefficients for lossy piezoelectric materials.

    PubMed

    Piquette, Jean C; McLaughlin, Elizabeth A

    2009-04-01

    Two competing approaches for calculating coupling coefficients for lossy piezoelectric materials, one producing a real result and the other a complex result, are compared and analyzed. It is found that the complex coupling coefficient suffers from mathematical difficulties, which the real coupling coefficient does not exhibit. Moreover, it is pointed out that a prediction made by the complex coupling coefficient theory conflicts with experiment while the corresponding real coupling coefficient theory prediction does not. When a coupling coefficient of interest has been computed from the real coupling coefficient theory using piezoelectric equations having intensive independent variables, the resulting expression has the same algebraic form as the corresponding static coupling coefficient formula. Moreover, only the real parts of the piezoelectric, elastic, and dielectric material properties appear. PMID:19406711

  13. Coupled Dust-Lattice Modes in Magnetized Complex Plasmas

    SciTech Connect

    Farokhi, B.; Shahmansouri, M.

    2008-09-07

    Dust lattice wave modes in a one dimensional plasma crystal (formed by paramagnetic dust particles) suspended in the plasma sheath are studied. The ion flow in the sheath introduces 'ion wakes' below the crystal particles. The wave dispersion relations are found under the influence of inhomogeneous magnetic field, wake charge effect and equilibrium charge gradient. The expression for the wave dispersion relations clearly show that three branches exist as a result of the coupling of longitudinal and transverse modes due to the Lorenz forces, charge gradient and wake charge effect. We observe a new coupling between the dust lattice modes, which have not reported so far.

  14. Coupling protein complex analysis to peptide based proteomics.

    PubMed

    Gao, Qiang; Madian, Ashraf G; Liu, Xiuping; Adamec, Jiri; Regnier, Fred E

    2010-12-01

    Proteolysis is a central component of most proteomics methods. Unfortunately much of the information relating to the structural diversity of proteins is lost during digestion. This paper describes a method in which the native proteome of yeast was subjected to preliminary fractionation by size exclusion chromatography (SEC) prior to trypsin digestion of SEC fractions and reversed phase chromatography-mass spectral analysis to identify tryptic peptides thus generated. Through this approach proteins associated with other proteins in high molecular mass complexes were recognized and identified. A focus of this work was on the identification of Hub proteins that associate with multiple interaction partners. A critical component of this strategy is to choose methods and conditions that maximize retention of native structure during the various stages of analysis prior to proteolysis, especially during cell lysis. Maximum survival of protein complexes during lysis was obtained with the French press and bead-beater methods of cell disruption at approximately pH 8 with 200 mM NaCl in the lysis buffer. Structure retention was favored by higher ionic strength, suggesting that hydrophobic effects are important in maintaining the structure of protein complexes. Recovery of protein complexes declined substantially with storage at any temperature, but storage at -20°C was best when low temperature storage was necessary. Slightly lower recovery was obtained with storage at -80°C while lowest recovery was achieved at 4°C. It was concluded that initial fractionation of native proteins in cell lysates by SEC prior to RPC-MS/MS of tryptic digests can be used to recognize and identify proteins in complexes along with their interaction partners in known protein complexes. PMID:21036361

  15. Understanding Complexity: Pattern Recognitions, Emergent Phenomena and Causal Coupling

    NASA Astrophysics Data System (ADS)

    Raia, F.

    2010-12-01

    In teaching and learning complex systems we face a fundamental issue: Simultaneity of causal interactions -where effects are at the same time causes of systems’ behavior. Complex systems’ behavior and evolution are controlled by negative and positive feedback processes, continually changing boundary conditions and complex interaction between systems levels (emergence). These processes cannot be described and understood in a mechanistic framework where causality is conceived of being mostly of cause-effect nature or a linear chain of causes and effects. Mechanist causality by definition is characterized by the assumption that an earlier phenomenon A has a causal effect on the development of a phenomenon B. Since this concept also assumes unidirectional time, B cannot have an effect on A. Since students study science mostly in the lingering mechanistic framework, they have problems understanding complex systems. Specifically, our research on students understanding of complexity indicates that our students seem to have great difficulties in explaining mechanisms underlying natural processes within the current paradigm. Students tend to utilize simple linear model of causality and establish a one-to-one correspondence between cause and effect describing phenomena such as emergence and self-organization as being mechanistically caused. Contrary to experts, when presented with data distribution -spatial and/or temporal-, students first consider or search for a unique cause without describing the distribution or a recognized pattern. Our research suggests that students do not consider a pattern observed as an emergent phenomenon and therefore a causal determinant influencing and controlling the evolution of the system. Changes in reasoning have been observed when students 1) are iteratively asked to recognize and describe patterns in data distribution and 2) subsequently learn to identify these patterns as emergent phenomena and as fundamental causal controls over

  16. Wind-Wave Coupling in a Complex Coastal Environment

    NASA Astrophysics Data System (ADS)

    Haus, B. K.; Laxague, N.; Ortiz-Suslow, D. G.; Graber, H. C.; Romeiser, R.

    2014-12-01

    The University of Miami's air-sea interaction research team has acquired, tested and successfully deployed polarimetric cameras on a variety of shipboard platforms. This has opened up a wide range of studies of processes at the air-sea interface that are critical for interpretation of remote sensing imagery in coastal regions. We can now resolve short wave spectra in the field fast enough to capture the wave growth and relaxation as the local wind gusts and wanes, the phase dependence short waves on longer waves and the effects of rain, wave breaking and surfactants on the ocean surface. Here we will present results from shipboard experiments in the Columbia River mouth and corresponding laboratory observations in the University of Miami's new Surge-Structure ATmosphere INteraction (SUSTAIN) laboratory that demonstrate the effects of topography and currents on surface waves and the corresponding air-sea coupling as observed in SAR imagery.

  17. Symmetrized complex amplitudes for He double photoionization from the time-dependent close coupling and exterior complex scaling methods

    SciTech Connect

    Horner, D.A.; Colgan, J.; Martin, F.; McCurdy, C.W.; Pindzola, M.S.; Rescigno, T.N.

    2004-06-01

    Symmetrized complex amplitudes for the double photoionization of helium are computed by the time-dependent close-coupling and exterior complex scaling methods, and it is demonstrated that both methods are capable of the direct calculation of these amplitudes. The results are found to be in excellent agreement with each other and in very good agreement with results of other ab initio methods and experiment.

  18. Towards quantification of vibronic coupling in photosynthetic antenna complexes

    NASA Astrophysics Data System (ADS)

    Singh, V. P.; Westberg, M.; Wang, C.; Dahlberg, P. D.; Gellen, T.; Gardiner, A. T.; Cogdell, R. J.; Engel, G. S.

    2015-06-01

    Photosynthetic antenna complexes harvest sunlight and efficiently transport energy to the reaction center where charge separation powers biochemical energy storage. The discovery of existence of long lived quantum coherence during energy transfer has sparked the discussion on the role of quantum coherence on the energy transfer efficiency. Early works assigned observed coherences to electronic states, and theoretical studies showed that electronic coherences could affect energy transfer efficiency—by either enhancing or suppressing transfer. However, the nature of coherences has been fiercely debated as coherences only report the energy gap between the states that generate coherence signals. Recent works have suggested that either the coherences observed in photosynthetic antenna complexes arise from vibrational wave packets on the ground state or, alternatively, coherences arise from mixed electronic and vibrational states. Understanding origin of coherences is important for designing molecules for efficient light harvesting. Here, we give a direct experimental observation from a mutant of LH2, which does not have B800 chromophores, to distinguish between electronic, vibrational, and vibronic coherence. We also present a minimal theoretical model to characterize the coherences both in the two limiting cases of purely vibrational and purely electronic coherence as well as in the intermediate, vibronic regime.

  19. Towards quantification of vibronic coupling in photosynthetic antenna complexes

    PubMed Central

    Singh, V. P.; Westberg, M.; Wang, C.; Dahlberg, P. D.; Gellen, T.; Gardiner, A. T.; Cogdell, R. J.

    2015-01-01

    Photosynthetic antenna complexes harvest sunlight and efficiently transport energy to the reaction center where charge separation powers biochemical energy storage. The discovery of existence of long lived quantum coherence during energy transfer has sparked the discussion on the role of quantum coherence on the energy transfer efficiency. Early works assigned observed coherences to electronic states, and theoretical studies showed that electronic coherences could affect energy transfer efficiency—by either enhancing or suppressing transfer. However, the nature of coherences has been fiercely debated as coherences only report the energy gap between the states that generate coherence signals. Recent works have suggested that either the coherences observed in photosynthetic antenna complexes arise from vibrational wave packets on the ground state or, alternatively, coherences arise from mixed electronic and vibrational states. Understanding origin of coherences is important for designing molecules for efficient light harvesting. Here, we give a direct experimental observation from a mutant of LH2, which does not have B800 chromophores, to distinguish between electronic, vibrational, and vibronic coherence. We also present a minimal theoretical model to characterize the coherences both in the two limiting cases of purely vibrational and purely electronic coherence as well as in the intermediate, vibronic regime. PMID:26049466

  20. Towards quantification of vibronic coupling in photosynthetic antenna complexes.

    PubMed

    Singh, V P; Westberg, M; Wang, C; Dahlberg, P D; Gellen, T; Gardiner, A T; Cogdell, R J; Engel, G S

    2015-06-01

    Photosynthetic antenna complexes harvest sunlight and efficiently transport energy to the reaction center where charge separation powers biochemical energy storage. The discovery of existence of long lived quantum coherence during energy transfer has sparked the discussion on the role of quantum coherence on the energy transfer efficiency. Early works assigned observed coherences to electronic states, and theoretical studies showed that electronic coherences could affect energy transfer efficiency--by either enhancing or suppressing transfer. However, the nature of coherences has been fiercely debated as coherences only report the energy gap between the states that generate coherence signals. Recent works have suggested that either the coherences observed in photosynthetic antenna complexes arise from vibrational wave packets on the ground state or, alternatively, coherences arise from mixed electronic and vibrational states. Understanding origin of coherences is important for designing molecules for efficient light harvesting. Here, we give a direct experimental observation from a mutant of LH2, which does not have B800 chromophores, to distinguish between electronic, vibrational, and vibronic coherence. We also present a minimal theoretical model to characterize the coherences both in the two limiting cases of purely vibrational and purely electronic coherence as well as in the intermediate, vibronic regime. PMID:26049466

  1. Towards quantification of vibronic coupling in photosynthetic antenna complexes

    SciTech Connect

    Singh, V. P.; Westberg, M.; Wang, C.; Gellen, T.; Engel, G. S.; Dahlberg, P. D.; Gardiner, A. T.; Cogdell, R. J.

    2015-06-07

    Photosynthetic antenna complexes harvest sunlight and efficiently transport energy to the reaction center where charge separation powers biochemical energy storage. The discovery of existence of long lived quantum coherence during energy transfer has sparked the discussion on the role of quantum coherence on the energy transfer efficiency. Early works assigned observed coherences to electronic states, and theoretical studies showed that electronic coherences could affect energy transfer efficiency—by either enhancing or suppressing transfer. However, the nature of coherences has been fiercely debated as coherences only report the energy gap between the states that generate coherence signals. Recent works have suggested that either the coherences observed in photosynthetic antenna complexes arise from vibrational wave packets on the ground state or, alternatively, coherences arise from mixed electronic and vibrational states. Understanding origin of coherences is important for designing molecules for efficient light harvesting. Here, we give a direct experimental observation from a mutant of LH2, which does not have B800 chromophores, to distinguish between electronic, vibrational, and vibronic coherence. We also present a minimal theoretical model to characterize the coherences both in the two limiting cases of purely vibrational and purely electronic coherence as well as in the intermediate, vibronic regime.

  2. Complex (dusty) plasmas—kinetic studies of strong coupling phenomenaa)

    NASA Astrophysics Data System (ADS)

    Morfill, Gregor E.; Ivlev, Alexei V.; Thomas, Hubertus M.

    2012-05-01

    "Dusty plasmas" can be found almost everywhere—in the interstellar medium, in star and planet formation, in the solar system in the Earth's atmosphere, and in the laboratory. In astrophysical plasmas, the dust component accounts for only about 1% of the mass, nevertheless this component has a profound influence on the thermodynamics, the chemistry, and the dynamics. Important physical processes are charging, sputtering, cooling, light absorption, and radiation pressure, connecting electromagnetic forces to gravity. Surface chemistry is another important aspect. In the laboratory, there is great interest in industrial processes (e.g., etching, vapor deposition) and—at the fundamental level—in the physics of strong coupling phenomena. Here, the dust (or microparticles) are the dominant component of the multi-species plasma. The particles can be observed in real time and space, individually resolved at all relevant length and time scales. This provides an unprecedented means for studying self-organisation processes in many-particle systems, including the onset of cooperative phenomena. Due to the comparatively large mass of the microparticles (10-12to10-9g), precision experiments are performed on the ISS. The following topics will be discussed: Phase transitions, phase separation, electrorheology, flow phenomena including the onset of turbulence at the kinetic level.

  3. Complex (dusty) plasmas-kinetic studies of strong coupling phenomena

    SciTech Connect

    Morfill, Gregor E.; Ivlev, Alexei V.; Thomas, Hubertus M.

    2012-05-15

    'Dusty plasmas' can be found almost everywhere-in the interstellar medium, in star and planet formation, in the solar system in the Earth's atmosphere, and in the laboratory. In astrophysical plasmas, the dust component accounts for only about 1% of the mass, nevertheless this component has a profound influence on the thermodynamics, the chemistry, and the dynamics. Important physical processes are charging, sputtering, cooling, light absorption, and radiation pressure, connecting electromagnetic forces to gravity. Surface chemistry is another important aspect. In the laboratory, there is great interest in industrial processes (e.g., etching, vapor deposition) and-at the fundamental level-in the physics of strong coupling phenomena. Here, the dust (or microparticles) are the dominant component of the multi-species plasma. The particles can be observed in real time and space, individually resolved at all relevant length and time scales. This provides an unprecedented means for studying self-organisation processes in many-particle systems, including the onset of cooperative phenomena. Due to the comparatively large mass of the microparticles (10{sup -12}to10{sup -9}g), precision experiments are performed on the ISS. The following topics will be discussed: Phase transitions, phase separation, electrorheology, flow phenomena including the onset of turbulence at the kinetic level.

  4. Synchronization Experiments With A Global Coupled Model of Intermediate Complexity

    NASA Astrophysics Data System (ADS)

    Selten, Frank; Hiemstra, Paul; Shen, Mao-Lin

    2013-04-01

    In the super modeling approach an ensemble of imperfect models are connected through nudging terms that nudge the solution of each model to the solution of all other models in the ensemble. The goal is to obtain a synchronized state through a proper choice of connection strengths that closely tracks the trajectory of the true system. For the super modeling approach to be successful, the connections should be dense and strong enough for synchronization to occur. In this study we analyze the behavior of an ensemble of connected global atmosphere-ocean models of intermediate complexity. All atmosphere models are connected to the same ocean model through the surface fluxes of heat, water and momentum, the ocean is integrated using weighted averaged surface fluxes. In particular we analyze the degree of synchronization between the atmosphere models and the characteristics of the ensemble mean solution. The results are interpreted using a low order atmosphere-ocean toy model.

  5. Handling Qualities of Model Reference Adaptive Controllers with Varying Complexity for Pitch-Roll Coupled Failures

    NASA Technical Reports Server (NTRS)

    Schaefer, Jacob; Hanson, Curt; Johnson, Marcus A.; Nguyen, Nhan

    2011-01-01

    Three model reference adaptive controllers (MRAC) with varying levels of complexity were evaluated on a high performance jet aircraft and compared along with a baseline nonlinear dynamic inversion controller. The handling qualities and performance of the controllers were examined during failure conditions that induce coupling between the pitch and roll axes. Results from flight tests showed with a roll to pitch input coupling failure, the handling qualities went from Level 2 with the baseline controller to Level 1 with the most complex MRAC tested. A failure scenario with the left stabilator frozen also showed improvement with the MRAC. Improvement in performance and handling qualities was generally seen as complexity was incrementally added; however, added complexity usually corresponds to increased verification and validation effort required for certification. The tradeoff between complexity and performance is thus important to a controls system designer when implementing an adaptive controller on an aircraft. This paper investigates this relation through flight testing of several controllers of vary complexity.

  6. Comment on the relation between the nonadiabatic coupling and the complex intersection of potential energy curves

    NASA Technical Reports Server (NTRS)

    Jaffe, R. L.

    1977-01-01

    Simple relations are discussed that provide a correspondence between the complex intersection of two potential surfaces and the nonadiabatic coupling matrix element between those surfaces. These are key quantities in semiclassical and quantum mechanical theories of collision induced electronic transitions. Within the two state approximation, the complex intersection is shown to be directly related to the location and magnitude of the peak in the nonadiabatic coupling. Two cases are considered: the avoided crossing between two potential surfaces; and the spin orbit interaction due to a P-2 halogen atom. Comparisons are made between the results of the two-state model and the results of ab initio quantum chemical calculations.

  7. Mode-Coupling Instability in a Fluid Two-Dimensional Complex Plasma

    NASA Astrophysics Data System (ADS)

    Ivlev, A. V.; Zhdanov, S. K.; Lampe, M.; Morfill, G. E.

    2014-09-01

    A theory of the mode-coupling instability (MCI) in a fluid two-dimensional complex plasma is developed. In analogy to the point-wake model of the wake-mediated interactions commonly used to describe MCI in two-dimensional crystals, the layer-wake model is employed for fluids. It is demonstrated that the wake-induced coupling of wave modes occurs in both crystalline and fluid complex plasmas, but the confinement-density threshold, which determines the MCI onset in crystals, virtually disappears in fluids. The theory shows excellent qualitative agreement with available experiments and provides certain predictions to be verified.

  8. Generalized Projective Synchronization between Two Complex Networks with Time-Varying Coupling Delay

    NASA Astrophysics Data System (ADS)

    Sun, Mei; Zeng, Chang-Yan; Tian, Li-Xin

    2009-01-01

    Generalized projective synchronization (GPS) between two complex networks with time-varying coupling delay is investigated. Based on the Lyapunov stability theory, a nonlinear controller and adaptive updated laws are designed. Feasibility of the proposed scheme is proven in theory. Moreover, two numerical examples are presented, using the energy resource system and Lü's system [Physica A 382 (2007) 672] as the nodes of the networks. GPS between two energy resource complex networks with time-varying coupling delay is achieved. This study can widen the application range of the generalized synchronization methods and will be instructive for the demand-supply of energy resource in some regions of China.

  9. J(Si,H) Coupling Constants in Nonclassical Transition-Metal Silane Complexes.

    PubMed

    Scherer, Wolfgang; Meixner, Petra; Batke, Kilian; Barquera-Lozada, José E; Ruhland, Klaus; Fischer, Andreas; Eickerling, Georg; Eichele, Klaus

    2016-09-12

    We will outline that the sign and magnitude of J(Si,H) coupling constants provide a highly sensitive tool to measure the extent of Si-H bond activation in nonclassical silane complexes. Up to now, this structure-property relationship was obscured by erroneous J(Si,H) sign determinations in the literature. These new findings also help to identify the salient control parameters of the Si-H bond activation process in nonclassical silane complexes. PMID:27503583

  10. A coupled multi-block solution procedure for spray combustion in complex geometries

    NASA Technical Reports Server (NTRS)

    Chen, Kuo-Huey; Shuen, Jian-Shun

    1993-01-01

    Turbulent spray-combusting flow in complex geometries is presently treated by a coupled implicit procedure that employs finite-rate chemistry and real gas properties for combustion, as well as the stochastic separated model for spray and a multiblock treatment for complex geometries. Illustrative numerical tests conducted encompass a steady-state nonreacting backward-facing step flow, a premixed single-phase combustion flow, and spray combustion flow in a gas turbine combustor.

  11. The mechanism of coupling between electron transfer and proton translocation in respiratory complex I.

    PubMed

    Sazanov, Leonid A

    2014-08-01

    NADH-ubiquinone oxidoreductase (complex I) is the first and largest enzyme in the respiratory chain of mitochondria and many bacteria. It couples the transfer of two electrons between NADH and ubiquinone to the translocation of four protons across the membrane. Complex I is an L-shaped assembly formed by the hydrophilic (peripheral) arm, containing all the redox centres performing electron transfer and the membrane arm, containing proton-translocating machinery. Mitochondrial complex I consists of 44 subunits of about 1 MDa in total, whilst the prokaryotic enzyme is simpler and generally consists of 14 conserved "core" subunits. Recently we have determined the first atomic structure of the entire complex I, using the enzyme from Thermus thermophilus (536 kDa, 16 subunits, 9 Fe-S clusters, 64 TM helices). Structure suggests a unique coupling mechanism, with redox energy of electron transfer driving proton translocation via long-range (up to ~200 Å) conformational changes. It resembles a steam engine, with coupling elements (akin to coupling rods) linking parts of this molecular machine. PMID:24943718

  12. Solution of coupled integral equations for quantum scattering in the presence of complex potentials

    SciTech Connect

    Franz, Jan

    2015-01-15

    In this paper, we present a method to compute solutions of coupled integral equations for quantum scattering problems in the presence of a complex potential. We show how the elastic and absorption cross sections can be obtained from the numerical solution of these equations in the asymptotic region at large radial distances.

  13. Coupling centrality and authority of co-processing model on complex networks

    NASA Astrophysics Data System (ADS)

    Zhang, Zhanli; Li, Huibin

    2016-04-01

    Coupling centrality and authority of co-processing model on complex networks are investigated in this paper. As one crucial factor to determine the processing ability of nodes, the information flow with potential time lag is modeled by co-processing diffusion which couples the continuous time processing and the discrete diffusing dynamics. Exact results on master equation and stationary state are obtained to disclose the formation. Considering the influence of a node to the global dynamical behavior, coupling centrality and authority are introduced for each node, which determine the relative importance and authority of nodes in the diffusion process. Furthermore, the experimental results on large-scale complex networks confirm our analytical prediction.

  14. Magnetic Exchange Couplings in Heterodinuclear Complexes Based on Differential Local Spin Rotations.

    PubMed

    Joshi, Rajendra P; Phillips, Jordan J; Peralta, Juan E

    2016-04-12

    We analyze the performance of a new method for the calculation of magnetic exchange coupling parameters for the particular case of heterodinuclear transition metals complexes of Cu, Ni, and V. This method is based on a generalized perturbative approach which uses differential local spin rotations via formal Lagrange multipiers (Phillips, J. J.; Peralta, J. E. J. Chem. Phys. 2013, 138, 174115). The reliability of the calculated couplings has been assessed by comparing with results from traditional energy differences with different density functional approximations and with experimental values. Our results show that this method to calculate magnetic exchange couplings can be reliably used for heteronuclear transition metal complexes, and at the same time, that it is independent from the different mapping schemes used in energy difference methods. PMID:26953521

  15. Electrostatic effects on proton coupled electron transfer in oxomanganese complexes inspired by the oxygen-evolving complex of photosystem II.

    PubMed

    Amin, Muhamed; Vogt, Leslie; Vassiliev, Serguei; Rivalta, Ivan; Sultan, Mohammad M; Bruce, Doug; Brudvig, Gary W; Batista, Victor S; Gunner, M R

    2013-05-23

    The influence of electrostatic interactions on the free energy of proton coupled electron transfer in biomimetic oxomanganese complexes inspired by the oxygen-evolving complex (OEC) of photosystem II (PSII) are investigated. The reported study introduces an enhanced multiconformer continuum electrostatics (MCCE) model, parametrized at the density functional theory (DFT) level with a classical valence model for the oxomanganese core. The calculated pKa's and oxidation midpoint potentials (E(m)'s) match experimental values for eight complexes, indicating that purely electrostatic contributions account for most of the observed couplings between deprotonation and oxidation state transitions. We focus on pKa's of terminal water ligands in [Mn(II/III)(H2O)6](2+/3+) (1), [Mn(III)(P)(H2O)2](3-) (2, P = 5,10,15,20-tetrakis(2,6-dichloro-3-sulfonatophenyl)porphyrinato), [Mn2(IV,IV)(μ-O)2(terpy)2(H2O)2](4+) (3, terpy = 2,2':6',2″-terpyridine), and [Mn3(IV,IV,IV)(μ-O)4(phen)4(H2O)2](4+) (4, phen = 1,10-phenanthroline) and the pKa's of μ-oxo bridges and Mn E(m)'s in [Mn2(μ-O)2(bpy)4] (5, bpy = 2,2'-bipyridyl), [Mn2(μ-O)2(salpn)2] (6, salpn = N,N'-bis(salicylidene)-1,3-propanediamine), [Mn2(μ-O)2(3,5-di(Cl)-salpn)2] (7), and [Mn2(μ-O)2(3,5-di(NO2)-salpn)2] (8). The analysis of complexes 6-8 highlights the strong coupling between electron and proton transfers, with any Mn oxidation lowering the pKa of an oxo bridge by 10.5 ± 0.9 pH units. The model also accounts for changes in the E(m)'s by ligand substituents, such as found in complexes 6-8, due to the electron withdrawing Cl (7) and NO2 (8). The reported study provides the foundation for analysis of electrostatic effects in other oxomanganese complexes and metalloenzymes, where proton coupled electron transfer plays a fundamental role in redox-leveling mechanisms. PMID:23570540

  16. π-π Stacking and ferromagnetic coupling mechanism on a binuclear Cu(II) complex.

    PubMed

    Chi, Yan-Hui; Yu, Li; Shi, Jing-Min; Zhang, Yi-Quan; Hu, Tai-Qiu; Zhang, Gui-Qiu; Shi, Wei; Cheng, Peng

    2011-02-21

    The ferromagnetic couplings were observed in an unpublished crystal that consists of binuclear copper(II) complexes, namely, [Cu(2)(μ(1,3)-SCN)(2)(PhenOH)(OCH(3))(2)(HOCH(3))(2)] (PhenOH = 2-hydroxy-1,10-phenanthroline), and in the binuclear complex Cu(ii) ion assumes a distorted octahedral geometry and thiocyanate anion functions as a μ(1,3)-SCN(-) equatorial-axial (EA) bridging ligand. The analysis for the crystal structure indicates that there are three types of magnetic coupling pathways, in which two pathways involve π-π stacking between the adjacent complexes and the third one is the μ(1,3)-SCN(-) bridged pathway. The fitting for the data of the variable-temperature magnetic susceptibilities shows that there is a ferromagnetic coupling between adjacent Cu(II) ions with J = 50.02 cm(-1). Theoretical calculations reveal that the two types of π-π stacking resulted in ferromagnetic couplings with J = 4.16 cm(-1) and J = 2.75 cm(-1), respectively, and the bridged thiocyanate anions pathway led to a weaker ferromagnetic interaction with J = 0.88 cm(-1). The theoretical calculations also indicate that the ferromagnetic coupling sign from the two types of π-π stacking does not accord with McConnell I spin-polarization mechanism. The analysis for the Wiberg bond indexes that originate from the π-π stacking atoms indicates that the Wiberg bond indexes are relevant to the associated magnetic coupling magnitude and the Wiberg bond index is one of the key factors that dominates the associated magnetic coupling magnitude. PMID:21212898

  17. Spin Adapted versus Broken Symmetry Approaches in the Description of Magnetic Coupling in Heterodinuclear Complexes.

    PubMed

    Costa, Ramon; Valero, Rosendo; Reta Mañeru, Daniel; Moreira, Ibério de P R; Illas, Francesc

    2015-03-10

    The performance of a series of wave function and density functional theory based methods in predicting the magnetic coupling constant of a family of heterodinuclear magnetic complexes has been studied. For the former, the accuracy is similar to other simple cases involving homodinuclear complexes, the main limitation being a sufficient inclusion of dynamical correlation effects. Nevertheless, these series of calculations provide an appropriate benchmark for density functional theory based methods. Here, the usual broken symmetry approach provides a convenient framework to predict the magnetic coupling constants but requires deriving the appropriate mapping. At variance with simple dinuclear complexes, spin projection based techniques cannot recover the corresponding (approximate) spin adapted solution. Present results also show that current implementation of spin flip techniques leads to unphysical results. PMID:26579753

  18. Characterizing and Modeling the Noise and Complex Impedance of Feedhorn-Coupled TES Polarimeters

    SciTech Connect

    Appel, J. W.; Beall, J. A.; Essinger-Hileman, T.; Parker, L. P.; Staggs, S. T.; Visnjic, C.; Zhao, Y.; Austermann, J. E.; Halverson, N. W.; Henning, J. W.; Simon, S. M.; Becker, D.; Britton, J.; Cho, H. M.; Hilton, G. C.; Irwin, K. D.; Niemack, M. D.; Yoon, K. W.; Benson, B. A.; Bleem, L. E.

    2009-12-16

    We present results from modeling the electrothermal performance of feedhorn-coupled transition edge sensor (TES) polarimeters under development for use in cosmic microwave background (CMB) polarization experiments. Each polarimeter couples radiation from a corrugated feedhorn through a planar orthomode transducer, which transmits power from orthogonal polarization modes to two TES bolometers. We model our TES with two- and three-block thermal architectures. We fit the complex impedance data at multiple points in the TES transition. From the fits, we predict the noise spectra. We present comparisons of these predictions to the data for two TESes on a prototype polarimeter.

  19. Efficient oxidative coupling of 2,6-disubstituted phenol catalyzed by a dicopper(II) complex.

    PubMed

    Liao, Bei-Sih; Liu, Yi-Hung; Peng, Shei-Ming; Liu, Shiuh-Tzung

    2012-01-28

    Complexation of a rigid multi-pyridine ligand bis(2-pyridyl)-1,8-naphthyridine (bpnp) with [Cu(2)(TFA)(4)] (TFA = trifluoroacetate) resulted in the formation of a dinuclear copper(II) complex, namely [Cu(2)(bpnp)(μ-OH)(TFA)(3)] (1). This complex has been characterized by X-ray crystallographic, spectroscopic and elemental analyses. Complex 1 is an efficient catalyst for the oxidative coupling of various 2,6-disubstituted phenols with molecular oxygen. Yields and selectivity depend on the reaction conditions employed, the best results being obtained in isopropanol or dioxane at 90 °C with yields of >99%. Mechanistic pathway of the catalysis is discussed. PMID:22116574

  20. anQCD: Fortran programs for couplings at complex momenta in various analytic QCD models

    NASA Astrophysics Data System (ADS)

    Ayala, César; Cvetič, Gorazd

    2016-02-01

    We provide three Fortran programs which evaluate the QCD analytic (holomorphic) couplings Aν(Q2) for complex or real squared momenta Q2. These couplings are holomorphic analogs of the powers a(Q2)ν of the underlying perturbative QCD (pQCD) coupling a(Q2) ≡αs(Q2) / π, in three analytic QCD models (anQCD): Fractional Analytic Perturbation Theory (FAPT), Two-delta analytic QCD (2 δanQCD), and Massive Perturbation Theory (MPT). The index ν can be noninteger. The provided programs do basically the same job as the Mathematica package anQCD.m published by us previously (Ayala and Cvetič, 2015), but are now written in Fortran.

  1. Application of coupled-channel Complex Scaling Method to {Lambda}(1405)

    SciTech Connect

    Dote, Akinobu; Myo, Takayuki

    2011-10-21

    We have applied the coupled-channel Complex Scaling Method (ccCSM) to the excited baryon {Lambda}(1405) which is the important building block of kaonic nuclei. {Lambda}(1405) is treated as a resonant state of the meson-baryon coupled system, K-barN and {pi}{Sigma}. In this article, it is reported that the ccCSM works well even with an energy-dependent K-barN potential such as a chiral SU(3)-based potential. We have tested two cases: the self-consistency condition is imposed on I) real energy and II) complex energy. Then, the self-consistent solutions are obtained in both cases in the framework of the ccCSM.

  2. Assessing spatial coupling in complex population dynamics using mutual prediction and continuity statistics

    USGS Publications Warehouse

    Nichols, J.M.; Moniz, L.; Nichols, J.D.; Pecora, L.M.; Cooch, E.

    2005-01-01

    A number of important questions in ecology involve the possibility of interactions or ?coupling? among potential components of ecological systems. The basic question of whether two components are coupled (exhibit dynamical interdependence) is relevant to investigations of movement of animals over space, population regulation, food webs and trophic interactions, and is also useful in the design of monitoring programs. For example, in spatially extended systems, coupling among populations in different locations implies the existence of redundant information in the system and the possibility of exploiting this redundancy in the development of spatial sampling designs. One approach to the identification of coupling involves study of the purported mechanisms linking system components. Another approach is based on time series of two potential components of the same system and, in previous ecological work, has relied on linear cross-correlation analysis. Here we present two different attractor-based approaches, continuity and mutual prediction, for determining the degree to which two population time series (e.g., at different spatial locations) are coupled. Both approaches are demonstrated on a one-dimensional predator?prey model system exhibiting complex dynamics. Of particular interest is the spatial asymmetry introduced into the model as linearly declining resource for the prey over the domain of the spatial coordinate. Results from these approaches are then compared to the more standard cross-correlation analysis. In contrast to cross-correlation, both continuity and mutual prediction are clearly able to discern the asymmetry in the flow of information through this system.

  3. Studying Arsenite-Humic Acid Complexation Using Size Exclusion Chromatography-Inductively Coupled Plasma Mass Spectrometry

    PubMed Central

    Liu, Guangliang; Cai, Yong

    2012-01-01

    Arsenic (As) can form complexes with dissolved organic matter (DOM), which affects the fate of arsenic in waste sites and natural environments. It remains a challenge to analyze DOM-bound As, in particular by using a direct chromatographic separation method. Size exclusion chromatography (SEC) hyphenated with UV spectrophotometer and inductively coupled plasma mass spectrometry (ICP-MS) was developed to characterize the complexation of arsenite (AsIII) with DOM. This SEC-UV-ICP-MS method is able to differentiate AsIII-DOM complexes from free As species and has the advantage of direct determination of both free and DOM-bound AsIII through mild separation. The suitability of this method for studying AsIII-DOM complexation was demonstrated by its application, in combination with the Scatchard plot and nonlinear regression of ligand binding model, for characterizing AsIII complexation with humic acid (HA) in the absence or presence of natural sand. The results suggest that, consistent with polyelectrolytic nature of HA, the AsIII-HA complexation should be accounted for by multiple classes of binding sites. By loosely classifying the binding sites into strong (S1) and weak (S2) sites, the apparent stability constants (Ks) of the resulting As-DOM complexes were calculated as log Ks1 = 6.5–7.1 while log Ks2 = 4.7–5.0. PMID:22664255

  4. Flexible simulation framework to couple processes in complex 3D models for subsurface utilization assessment

    NASA Astrophysics Data System (ADS)

    Kempka, Thomas; Nakaten, Benjamin; De Lucia, Marco; Nakaten, Natalie; Otto, Christopher; Pohl, Maik; Tillner, Elena; Kühn, Michael

    2016-04-01

    Utilization of the geological subsurface for production and storage of hydrocarbons, chemical energy and heat as well as for waste disposal requires the quantification and mitigation of environmental impacts as well as the improvement of georesources utilization in terms of efficiency and sustainability. The development of tools for coupled process simulations is essential to tackle these challenges, since reliable assessments are only feasible by integrative numerical computations. Coupled processes at reservoir to regional scale determine the behaviour of reservoirs, faults and caprocks, generally demanding for complex 3D geological models to be considered besides available monitoring and experimenting data in coupled numerical simulations. We have been developing a flexible numerical simulation framework that provides efficient workflows for integrating the required data and software packages to carry out coupled process simulations considering, e.g., multiphase fluid flow, geomechanics, geochemistry and heat. Simulation results are stored in structured data formats to allow for an integrated 3D visualization and result interpretation as well as data archiving and its provision to collaborators. The main benefits in using the flexible simulation framework are the integration of data geological and grid data from any third party software package as well as data export to generic 3D visualization tools and archiving formats. The coupling of the required process simulators in time and space is feasible, while different spatial dimensions in the coupled simulations can be integrated, e.g., 0D batch with 3D dynamic simulations. User interaction is established via high-level programming languages, while computational efficiency is achieved by using low-level programming languages. We present three case studies on the assessment of geological subsurface utilization based on different process coupling approaches and numerical simulations.

  5. COUPLING

    DOEpatents

    Hawke, B.C.

    1963-02-26

    This patent relates to a releasable coupling connecting a control rod to a control rod drive. This remotely operable coupling mechanism can connect two elements which are laterally and angviarly misaligned, and provides a means for sensing the locked condition of the elements. The coupling utilizes a spherical bayonet joint which is locked against rotation by a ball detent lock. (AEC)

  6. Robust synchronization of complex networks with uncertain couplings and incomplete information

    NASA Astrophysics Data System (ADS)

    Wang, Fan; Liang, Jinling; Wang, Zidong; Alsaadi, Fuad E.

    2016-07-01

    The mean square exponential (MSE) synchronization problem is investigated in this paper for complex networks with simultaneous presence of uncertain couplings and incomplete information, which comprise both the randomly occurring delay and the randomly occurring non-linearities. The network considered is uncertain with time-varying stochastic couplings. The randomly occurring delay and non-linearities are modelled by two Bernoulli-distributed white sequences with known probabilities to better describe realistic complex networks. By utilizing the coordinate transformation, the addressed complex network can be exponentially synchronized in the mean square if the MSE stability of a transformed subsystem can be assured. The stability problem is studied firstly for the transformed subsystem based on the Lyapunov functional method. Then, an easy-to-verify sufficient criterion is established by further decomposing the transformed system, which embodies the joint impacts of the single-node dynamics, the network topology and the statistical quantities of the uncertainties on the synchronization of the complex network. Numerical examples are exploited to illustrate the effectiveness of the proposed methods.

  7. Ruthenium tris(bipyridine) complexes with sulfur substituents: model studies for PEG coupling.

    PubMed

    Fiore, Gina L; Goguen, Brenda N; Klinkenberg, Jessica L; Payne, Sarah J; Demas, J N; Fraser, Cassandra L

    2008-07-21

    Ruthenium polypyridyl complexes are incorporated into polymers for sensing and light emitting materials applications. Coupling reactions between metal complexes and polymers are one route to polymeric metal complexes. In an effort to increase conjugation efficiency, tune materials properties, and introduce a responsive crosslink, ruthenium tris(bipyridine) derivatives with sulfur substituents were synthesized and compared to oxygen analogues. Difunctional thiols, thioesters, thioethers, and disulfides, as well as hexafunctional nonpolymeric model systems, were explored. Upon exposure to oxygen, the thiol derivative was readily oxidized. These studies guided Ru(bpy)3 PEG coupling reactions with disulfide and thioether linkages, which proceeded to approximately 80% and approximately 60% yield, respectively. The luminescence properties of the Ru PEG derivatives and model systems were investigated. The emission spectra and lifetimes for all complexes in CH3CN under an inert atmosphere are comparable to [Ru(bpy)3]Cl2. Lifetime data for nonpolymeric analogues fit to a single exponential decay indicating heterogeneity, suggesting sample homogeneity, whereas data for polymers fit to a multiexponential decay. In contrast to certain [Ru(bpy)3](2+)/thiol mixtures, no intramolecular quenching by the sulfide is observed for [Ru(bpy)2{bpy(CH2SH)2}](PF6)2. Emission spectra red shift and multiexponential decay are noted for the oxidized Ru thiol product. The rates of oxygen quenching are slower for Ru PEG derivatives than those for nonpolymeric analogues, which may be attributed to shielding effects of the polymer chain. PMID:18563893

  8. Semiquinone intermediates are involved in the energy coupling mechanism of E. coli complex I.

    PubMed

    Narayanan, Madhavan; Leung, Steven A; Inaba, Yuta; Elguindy, Mahmoud M; Nakamaru-Ogiso, Eiko

    2015-08-01

    Complex I (NADH:quinone oxidoreductase) is central to cellular aerobic energy metabolism, and its deficiency is involved in many human mitochondrial diseases. Complex I translocates protons across the membrane using electron transfer energy. Semiquinone (SQ) intermediates appearing during catalysis are suggested to be key for the coupling mechanism in complex I. However, the existence of SQ has remained controversial due to the extreme difficulty in detecting unstable and low intensity SQ signals. Here, for the first time with Escherichia coli complex I reconstituted in proteoliposomes, we successfully resolved and characterized three distinct SQ species by EPR. These species include: fast-relaxing SQ (SQNf) with P1/2 (half-saturation power level)>50mW and a wider linewidth (12.8 G); slow-relaxing SQ (SQNs) with P1/2=2-3mW and a 10G linewidth; and very slow-relaxing SQ (SQNvs) with P1/2= ~0.1mW and a 7.5G linewidth. The SQNf signals completely disappeared in the presence of the uncoupler gramicidin D or squamotacin, a potent E. coli complex I inhibitor. The pH dependency of the SQNf signals correlated with the proton-pumping activities of complex I. The SQNs signals were insensitive to gramicidin D, but sensitive to squamotacin. The SQNvs signals were insensitive to both gramicidin D and squamotacin. Our deuterium exchange experiments suggested that SQNf is neutral, while SQNs and SQNvs are anion radicals. The SQNs signals were lost in the ΔNuoL mutant missing transporter module subunits NuoL and NuoM. The roles and relationships of the SQ intermediates in the coupling mechanism are discussed. PMID:25868873

  9. Complex spectrum of finite-density lattice QCD with static quarks at strong coupling

    NASA Astrophysics Data System (ADS)

    Nishimura, Hiromichi; Ogilvie, Michael C.; Pangeni, Kamal

    2016-05-01

    We calculate the spectrum of transfer matrix eigenvalues associated with Polyakov loops in finite-density lattice QCD with static quarks. These eigenvalues determine the spatial behavior of Polyakov loop correlation functions. Our results are valid for all values of the gauge coupling in 1 +1 dimensions and in the strong-coupling region for any number of dimensions. When the quark chemical potential μ is nonzero, the spatial transfer matrix Ts is non-Hermitian. The appearance of complex eigenvalues in Ts is a manifestation of the sign problem in finite-density QCD. The invariance of finite-density QCD under the combined action of charge conjugation C and complex conjugation K implies that the eigenvalues of Ts are either real or part of a complex pair. Calculation of the spectrum confirms the existence of complex pairs in much of the temperature-chemical potential plane. Many features of the spectrum for static quarks are determined by a particle-hole symmetry. For μ that is small compared to the quark mass M , we typically find real eigenvalues for the lowest-lying states. At somewhat larger values of μ , pairs of eigenvalues may form complex-conjugate pairs, leading to damped oscillatory behavior in Polyakov loop correlation functions. However, near μ =M , the low-lying spectrum becomes real again. This is a direct consequence of the approximate particle-hole symmetry at μ =M for heavy quarks. This behavior of the eigenvalues should be observable in lattice simulations and can be used as a test of lattice algorithms. Our results provide independent confirmation of results we have previously obtained in Polyakov-Nambu-Jona-Lasinio models using complex saddle points.

  10. Complex dynamics analysis of impulsively coupled Duffing oscillators with ring structure

    NASA Astrophysics Data System (ADS)

    Jiang, Hai-Bo; Zhang, Li-Ping; Yu, Jian-Jiang

    2015-02-01

    Impulsively coupled systems are high-dimensional non-smooth systems that can exhibit rich and complex dynamics. This paper studies the complex dynamics of a non-smooth system which is unidirectionally impulsively coupled by three Duffing oscillators in a ring structure. By constructing a proper Poincaré map of the non-smooth system, an analytical expression of the Jacobian matrix of Poincaré map is given. Two-parameter Hopf bifurcation sets are obtained by combining the shooting method and the Runge-Kutta method. When the period is fixed and the coupling strength changes, the system undergoes stable, periodic, quasi-periodic, and hyper-chaotic solutions, etc. Floquet theory is used to study the stability of the periodic solutions of the system and their bifurcations. Project supported by the National Natural Science Foundation of China (Grant Nos. 11402224, 11202180, 61273106, and 11171290), the Qing Lan Project of the Jiangsu Higher Educational Institutions of China, and the Jiangsu Overseas Research and Training Program for University Prominent Young and Middle-aged Teachers and Presidents.

  11. The Ndc80 complex uses a tripartite attachment point to couple microtubule depolymerization to chromosome movement

    PubMed Central

    Tooley, John G.; Miller, Stephanie A.; Stukenberg, P. Todd

    2011-01-01

    In kinetochores, the Ndc80 complex couples the energy in a depolymerizing microtubule to perform the work of moving chromosomes. The complex directly binds microtubules using an unstructured, positively charged N-terminal tail located on Hec1/Ndc80. Hec1/Ndc80 also contains a calponin homology domain (CHD) that increases its affinity for microtubules in vitro, yet whether it is required in cells and how the tail and CHD work together are critical unanswered questions. Human kinetochores containing Hec1/Ndc80 with point mutations in the CHD fail to align chromosomes or form productive microtubule attachments. Kinetochore architecture and spindle checkpoint protein recruitment are unaffected in these mutants, and the loss of CHD function cannot be rescued by removing Aurora B sites from the tail. The interaction between the Hec1/Ndc80 CHD and a microtubule is facilitated by positively charged amino acids on two separate regions of the CHD, and both are required for kinetochores to make stable attachments to microtubules. Chromosome congression in cells also requires positive charge on the Hec1 tail to facilitate microtubule contact. In vitro binding data suggest that charge on the tail regulates attachment by directly increasing microtubule affinity as well as driving cooperative binding of the CHD. These data argue that in vertebrates there is a tripartite attachment point facilitating the interaction between Hec1/Ndc80 and microtubules. We discuss how such a complex microtubule-binding interface may facilitate the coupling of depolymerization to chromosome movement. PMID:21325630

  12. Proton coupled electron transfer from the excited state of a ruthenium(II) pyridylimidazole complex.

    PubMed

    Pannwitz, Andrea; Wenger, Oliver S

    2016-04-28

    Proton coupled electron transfer (PCET) from the excited state of [Ru(bpy)2pyimH](2+) (bpy = 2,2'-bipyridine; pyimH = 2-(2'-pyridyl)imidazole) to N-methyl-4,4'-bipyridinium (monoquat, MQ(+)) was studied. While this complex has been investigated previously, our study is the first to show that the formal bond dissociation free energy (BDFE) of the imidazole-N-H bond decreases from (91 ± 1) kcal mol(-1) in the electronic ground state to (43 ± 5) kcal mol(-1) in the lowest-energetic (3)MLCT excited state. This makes the [Ru(bpy)2pyimH](2+) complex a very strong (formal) hydrogen atom donor even when compared to metal hydride complexes, and this is interesting for light-driven (formal) hydrogen atom transfer (HAT) reactions with a variety of different substrates. Mechanistically, formal HAT between (3)MLCT excited [Ru(bpy)2pyimH](2+) and monoquat in buffered 1 : 1 (v : v) CH3CN/H2O was found to occur via a sequence of reaction steps involving electron transfer from Ru(ii) to MQ(+) coupled to release of the N-H proton to buffer base, followed by protonation of reduced MQ(+) by buffer acid. Our study is relevant in the larger contexts of photoredox catalysis and light-to-chemical energy conversion. PMID:27094541

  13. Substrate-Na{sup +} complex formation: Coupling mechanism for {gamma}-aminobutyrate symporters

    SciTech Connect

    Pallo, Anna; Simon, Agnes; Bencsura, Akos; Heja, Laszlo; Kardos, Julianna

    2009-07-24

    Crystal structures of transmembrane transport proteins belonging to the important families of neurotransmitter-sodium symporters reveal how they transport neurotransmitters across membranes. Substrate-induced structural conformations of gated neurotransmitter-sodium symporters have been in the focus of research, however, a key question concerning the mechanism of Na{sup +} ion coupling remained unanswered. Homology models of human glial transporter subtypes of the major inhibitory neurotransmitter {gamma}-aminobutyric acid were built. In accordance with selectivity data for subtype 2 vs. 3, docking and molecular dynamics calculations suggest similar orthosteric substrate (inhibitor) conformations and binding crevices but distinguishable allosteric Zn{sup 2+} ion binding motifs. Considering the occluded conformational states of glial human {gamma}-aminobutyric acid transporter subtypes, we found major semi-extended and minor ring-like conformations of zwitterionic {gamma}-aminobutyric acid in complex with Na{sup +} ion. The existence of the minor ring-like conformation of {gamma}-aminobutyric acid in complex with Na{sup +} ion may be attributed to the strengthening of the intramolecular H-bond by the electrostatic effect of Na{sup +} ion. Coupling substrate uptake into cells with the thermodynamically favorable Na{sup +} ion movement through substrate-Na{sup +} ion complex formation may be a mechanistic principle featuring transmembrane neurotransmitter-sodium symporter proteins.

  14. Higher spin gravitational couplings: Ghosts in the Yang-Mills detour complex

    SciTech Connect

    Gover, A. R.; Hallowell, K.; Waldron, A.

    2007-01-15

    Gravitational interactions of higher spin fields are generically plagued by inconsistencies. There exists however, a simple framework that couples higher spins to a broad class of gravitational backgrounds (including Ricci flat and Einstein) consistently at the classical level. The model is the simplest example of a Yang-Mills detour complex and has broad mathematical applications, especially to conformal geometry. Even the simplest version of the theory, which couples gravitons, vectors and scalar fields in a flat background is rather rich, providing an explicit setting for detailed analysis of ghost excitations. Its asymptotic scattering states consist of a physical massless graviton, scalar, and massive vector along with a degenerate pair of zero norm photon excitations. Coherent states of the unstable sector do have positive norms, but their evolution is no longer unitary and amplitudes grow with time. The class of models proposed is extremely general and of considerable interest for ghost condensation and invariant theory.

  15. Ruthenium Carbon-Rich Complexes as Redox Switchable Metal Coupling Units.

    PubMed

    Di Piazza, Emmanuel; Merhi, Areej; Norel, Lucie; Choua, Sylvie; Turek, Philippe; Rigaut, Stéphane

    2015-07-01

    With the help of EPR spectroscopy, we show that the diamagnetic [Ru(dppe)2(-C≡C-R)2] system sets up a magnetic coupling between two organic radicals R, i.e., two nitronyl nitroxide or two verdazyl units, which is stronger than that of related platinum organometallic systems. Surprisingly, further oxidation of the ruthenium redox-active metal coupling unit (MCU), which introduces an additional spin unit on the carbon-rich part, leads to the switching off of this interaction. On the contrary, in simpler complexes bearing only one of the organic radical ligands [C6H5-C≡C-Ru(dppe)2-C≡C-R], one-electron oxidation of the transition metal unit generates an interaction between the two spin carriers of comparable magnitude to that observed in the above corresponding neutral systems. PMID:26068041

  16. Direct C-C coupling of two Ni-salphen complexes to yield dinickel-disalphen complexes with symmetric and non-symmetric substitution-patterns.

    PubMed

    Bugenhagen, B E C; Prosenc, M H

    2016-04-25

    The synthesis of symmetric and non-symmetric 5,5'-linked disalophen Ni(ii) complexes by the Suzuki-Miyaura-reaction is reported. Also, the synthesis and structural characterization of four Ni(ii)-precursor complexes are presented. The 5-Br-substituted mononuclear complexes and are coupled to the pinacolborane substituted complexes and yielding the four dinuclear dinickel complexes in good yields. The crystal structure of dinuclear complex was obtained revealing a coplanar arrangement between the two salophen fragments. Electronic spectra as well as DFT-calculations on the ground states and excitation energies are reported and they reveal a small coupling between the electronically saturated Ni-salophen complexes. PMID:27040080

  17. Coupled variable selection for regression modeling of complex treatment patterns in a clinical cancer registry.

    PubMed

    Schmidtmann, I; Elsäßer, A; Weinmann, A; Binder, H

    2014-12-30

    For determining a manageable set of covariates potentially influential with respect to a time-to-event endpoint, Cox proportional hazards models can be combined with variable selection techniques, such as stepwise forward selection or backward elimination based on p-values, or regularized regression techniques such as component-wise boosting. Cox regression models have also been adapted for dealing with more complex event patterns, for example, for competing risks settings with separate, cause-specific hazard models for each event type, or for determining the prognostic effect pattern of a variable over different landmark times, with one conditional survival model for each landmark. Motivated by a clinical cancer registry application, where complex event patterns have to be dealt with and variable selection is needed at the same time, we propose a general approach for linking variable selection between several Cox models. Specifically, we combine score statistics for each covariate across models by Fisher's method as a basis for variable selection. This principle is implemented for a stepwise forward selection approach as well as for a regularized regression technique. In an application to data from hepatocellular carcinoma patients, the coupled stepwise approach is seen to facilitate joint interpretation of the different cause-specific Cox models. In conditional survival models at landmark times, which address updates of prediction as time progresses and both treatment and other potential explanatory variables may change, the coupled regularized regression approach identifies potentially important, stably selected covariates together with their effect time pattern, despite having only a small number of events. These results highlight the promise of the proposed approach for coupling variable selection between Cox models, which is particularly relevant for modeling for clinical cancer registries with their complex event patterns. PMID:25345575

  18. Multistability and complex dynamics in coupled semiconductor lasers with time-delayed feedback

    NASA Astrophysics Data System (ADS)

    Balakin, M.; Kochkurov, L.; Melnikov, L.; Astakhov, V.

    2016-04-01

    We investigate complex dynamics of two coupled nonidentical Land-Kobayashi oscillators. It is shown that at low values of feedback rate variation of delay only leads to alternation of periodic and stationary regimes. The analysis of characteristic regimes of the system in a wide range of parameters is provided. We demonstrate that the system under study is multistable. With the variation of control parameters sole fixed point repeatedly undergoes supercritical Andronov-Hopf bifurcations, which leads to an increase in the number of limit cycles co-existing in the phase space. It is shown that multistable states are formed by different combinations of the periodic, quasi-periodic and chaotic regimes.

  19. Complex transitions between spike, burst or chaos synchronization states in coupled neurons with coexisting bursting patterns

    NASA Astrophysics Data System (ADS)

    Gu, Hua-Guang; Chen, Sheng-Gen; Li, Yu-Ye

    2015-05-01

    We investigated the synchronization dynamics of a coupled neuronal system composed of two identical Chay model neurons. The Chay model showed coexisting period-1 and period-2 bursting patterns as a parameter and initial values are varied. We simulated multiple periodic and chaotic bursting patterns with non-(NS), burst phase (BS), spike phase (SS), complete (CS), and lag synchronization states. When the coexisting behavior is near period-2 bursting, the transitions of synchronization states of the coupled system follows very complex transitions that begins with transitions between BS and SS, moves to transitions between CS and SS, and to CS. Most initial values lead to the CS state of period-2 bursting while only a few lead to the CS state of period-1 bursting. When the coexisting behavior is near period-1 bursting, the transitions begin with NS, move to transitions between SS and BS, to transitions between SS and CS, and then to CS. Most initial values lead to the CS state of period-1 bursting but a few lead to the CS state of period-2 bursting. The BS was identified as chaos synchronization. The patterns for NS and transitions between BS and SS are insensitive to initial values. The patterns for transitions between CS and SS and the CS state are sensitive to them. The number of spikes per burst of non-CS bursting increases with increasing coupling strength. These results not only reveal the initial value- and parameter-dependent synchronization transitions of coupled systems with coexisting behaviors, but also facilitate interpretation of various bursting patterns and synchronization transitions generated in the nervous system with weak coupling strength. Project supported by the National Natural Science Foundation of China (Grant Nos. 11372224 and 11402039) and the Fundamental Research Funds for Central Universities designated to Tongji University (Grant No. 1330219127).

  20. Spin-coupling in ferric metalloporphyrin radical cation complexes: Mössbauer and susceptibility studies

    NASA Astrophysics Data System (ADS)

    Lang, George; Boso, Brian; Erler, Brian S.; Reed, Christopher A.

    1986-03-01

    The ferric metalloporphyrin π-radical cation complexes Fe(III) (OClO3)2 (TPP.) and [Fe(III) Cl (TPP.)] [SbCl6] were examined in microcrystalline form by Mössbauer spectroscopy and magnetic susceptometry over a range of temperatures and applied fields. All measurements on the six-coordinate Fe(OClO3)2 (TPP.) were consistent with isolated molecules having an S=5/2 iron site with zero field splitting (12 cm-1) S2z that is ferromagnetically coupled to the S=1/2 porphyrin radical by an energy term (-110 cm-1) Sṡs. Thus the ground state is overall spin-3. In the five-coordinate [FeCl (TPP.)] [SbCl6] the susceptibility is in reasonable agreement with the results of a calculation based on zero field splitting (12 cm-1) S2z for the S=5/2 iron and antiferromagnetic coupling (200 cm-1) Sṡs with the radical to give an overall spin-2 ground state. However, the Mössbauer measurements require a more complicated model having the same large intramolecular iron-radical coupling, a smaller zero field splitting (3 cm-1) S2z, and weak intermolecular antiferromagnetic coupling between heme pairs given by (32 cm-1) s1ṡs2 or, equivalently, (0.65 cm-1) S1ṡS2. A slightly improved correspondence with the measured susceptibility results. The intermolecular antiferromagnetic coupling probably results from crystallization of the [FeCl (TPP.)]+ cations in face-to-face dimers as observed in other closely related five-coordinate iron (III) porphyrins.

  1. Direct Modulation of Heterotrimeric G Protein-coupled Signaling by a Receptor Kinase Complex.

    PubMed

    Tunc-Ozdemir, Meral; Urano, Daisuke; Jaiswal, Dinesh Kumar; Clouse, Steven D; Jones, Alan M

    2016-07-01

    Plants and some protists have heterotrimeric G protein complexes that activate spontaneously without canonical G protein-coupled receptors (GPCRs). In Arabidopsis, the sole 7-transmembrane regulator of G protein signaling 1 (AtRGS1) modulates the G protein complex by keeping it in the resting state (GDP-bound). However, it remains unknown how a myriad of biological responses is achieved with a single G protein modulator. We propose that in complete contrast to G protein activation in animals, plant leucine-rich repeat receptor-like kinases (LRR RLKs), not GPCRs, provide this discrimination through phosphorylation of AtRGS1 in a ligand-dependent manner. G protein signaling is directly activated by the pathogen-associated molecular pattern flagellin peptide 22 through its LRR RLK, FLS2, and co-receptor BAK1. PMID:27235398

  2. Coupling of downstream RNA polymerase-promoter interactions with formation of catalytically competent transcription initiation complex

    PubMed Central

    Mekler, Vladimir; Minakhin, Leonid; Borukhov, Sergei; Mustaev, Arkady; Severinov, Konstantin

    2014-01-01

    Bacterial RNA polymerase (RNAP) makes extensive contacts with duplex DNA downstream of the transcription bubble in initiation and elongation complexes. We investigated the role of downstream interactions in formation of catalytically competent transcription initiation complex by measuring initiation activity of stable RNAP complexes with model promoter DNA fragments whose downstream ends extend from +3 to +21 relative to the transcription start site at +1. We found that DNA downstream of position +6 does not play a significant role in transcription initiation when RNAP-promoter interactions upstream of the transcription start site are strong and promoter melting region is AT-rich. Further shortening of downstream DNA dramatically reduces efficiency of transcription initiation. The boundary of minimal downstream DNA duplex needed for efficient transcription initiation shifted further away from the catalytic center upon increasing the GC content of promoter melting region or in the presence of bacterial stringent response regulators DksA and ppGpp. These results indicate that the strength of RNAP-downstream DNA interactions has to reach a certain threshold to retain the catalytically competent conformation of the initiation complex and that establishment of contacts between RNAP and downstream DNA can be coupled with promoter melting. The data further suggest that RNAP interactions with DNA immediately downstream of the transcription bubble are particularly important for initiation of transcription. We hypothesize that these active center-proximal contacts stabilize the DNA template strand in the active center cleft and/or position the RNAP clamp domain to allow RNA synthesis. PMID:25311862

  3. Chromate adsorption on selected soil minerals: Surface complexation modeling coupled with spectroscopic investigation.

    PubMed

    Veselská, Veronika; Fajgar, Radek; Číhalová, Sylva; Bolanz, Ralph M; Göttlicher, Jörg; Steininger, Ralph; Siddique, Jamal A; Komárek, Michael

    2016-11-15

    This study investigates the mechanisms of Cr(VI) adsorption on natural clay (illite and kaolinite) and synthetic (birnessite and ferrihydrite) minerals, including its speciation changes, and combining quantitative thermodynamically based mechanistic surface complexation models (SCMs) with spectroscopic measurements. Series of adsorption experiments have been performed at different pH values (3-10), ionic strengths (0.001-0.1M KNO3), sorbate concentrations (10(-4), 10(-5), and 10(-6)M Cr(VI)), and sorbate/sorbent ratios (50-500). Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and X-ray absorption spectroscopy were used to determine the surface complexes, including surface reactions. Adsorption of Cr(VI) is strongly ionic strength dependent. For ferrihydrite at pH <7, a simple diffuse-layer model provides a reasonable prediction of adsorption. For birnessite, bidentate inner-sphere complexes of chromate and dichromate resulted in a better diffuse-layer model fit. For kaolinite, outer-sphere complexation prevails mainly at lower Cr(VI) loadings. Dissolution of solid phases needs to be considered for better SCMs fits. The coupled SCM and spectroscopic approach is thus useful for investigating individual minerals responsible for Cr(VI) retention in soils, and improving the handling and remediation processes. PMID:27450335

  4. Impaired Astrocytic Gap Junction Coupling and Potassium Buffering in a Mouse Model of Tuberous Sclerosis Complex

    PubMed Central

    Xu, Lin; Zeng, Ling-Hui; Wong, Michael

    2009-01-01

    Abnormalities in astrocytes occur in the brains of patients with Tuberous Sclerosis Complex (TSC) and may contribute to the pathogenesis of neurological dysfunction in this disease. Here, we report that knock-out mice with Tsc1 gene inactivation in glia (Tsc1GFAPCKO mice) exhibit decreased expression of the astrocytic connexin protein, Cx43, and an associated impairment in gap junction coupling between astrocytes. Correspondingly, hippocampal slices from Tsc1GFAPCKO mice have increased extracellular potassium concentration in response to stimulation. This impaired potassium buffering can be attributed to abnormal gap junction coupling, as a gap junction inhibitor elicits an additional increase in potassium concentration in control, but not Tsc1GFAPCKO slices. Furthermore, treatment with a mammalian target of rapamycin inhibitor reverses the deficient Cx43 expression and impaired potassium buffering. These findings suggest that Tsc1 inactivation in astrocytes causes defects in astrocytic gap junction coupling and potassium clearance, which may contribute to epilepsy in Tsc1GFAPCKO mice. PMID:19385061

  5. COUPLING

    DOEpatents

    Frisch, E.; Johnson, C.G.

    1962-05-15

    A detachable coupling arrangement is described which provides for varying the length of the handle of a tool used in relatively narrow channels. The arrangement consists of mating the key and keyhole formations in the cooperating handle sections. (AEC)

  6. Reductive coupling of nitrogen monoxide (*NO) facilitated by heme/copper complexes.

    PubMed

    Wang, Jun; Schopfer, Mark P; Puiu, Simona C; Sarjeant, Amy A N; Karlin, Kenneth D

    2010-02-15

    The interactions of nitrogen monoxide (*NO; nitric oxide) with transition metal centers continue to be of great interest, in part due to their importance in biochemical processes. Here, we describe *NO((g)) reductive coupling chemistry of possible relevance to that process (i.e., nitric oxide reductase (NOR) biochemistry), which occurs at the heme/Cu active site of cytochrome c oxidases (CcOs). In this report, heme/Cu/*NO((g)) activity is studied using 1:1 ratios of heme and copper complex components, (F(8))Fe (F(8) = tetrakis(2,6-difluorophenyl)porphyrinate(2-)) and [(tmpa)Cu(I)(MeCN)](+) (TMPA = tris(2-pyridylmethyl)amine). The starting point for heme chemistry is the mononitrosyl complex (F(8))Fe(NO) (lambda(max) = 399 (Soret), 541 nm in acetone). Variable-temperature (1)H and (2)H NMR spectra reveal a broad peak at delta = 6.05 ppm (pyrrole) at room temperature (RT), which gives rise to asymmetrically split pyrrole peaks at 9.12 and 8.54 ppm at -80 degrees C. A new heme dinitrosyl species, (F(8))Fe(NO)(2), obtained by bubbling (F(8))Fe(NO) with *NO((g)) at -80 degrees C, could be reversibly formed, as monitored by UV-vis (lambda(max) = 426 (Soret), 538 nm in acetone), EPR (silent), and NMR spectroscopies; that is, the mono-NO complex was regenerated upon warming to RT. (F(8))Fe(NO)(2) reacts with [(tmpa)Cu(I)(MeCN)](+) and 2 equiv of acid to give [(F(8))Fe(III)](+), [(tmpa)Cu(II)(solvent)](2+), and N(2)O((g)), fitting the stoichiometric *NO((g)) reductive coupling reaction: 2*NO((g)) + Fe(II) + Cu(I) + 2H(+) --> N(2)O((g)) + Fe(III) + Cu(II) + H(2)O, equivalent to one enzyme turnover. Control reaction chemistry shows that both iron and copper centers are required for the NOR-type chemistry observed and that, if acid is not present, half the *NO is trapped as a (F(8))Fe(NO) complex, while the remaining nitrogen monoxide undergoes copper complex promoted disproportionation chemistry. As part of this study, [(F(8))Fe(III)]SbF(6) was synthesized and characterized

  7. Coupling Charge Reduction Mass Spectrometry to Liquid Chromatography for Complex Mixture Analysis.

    PubMed

    Stutzman, John R; Crowe, Matthew C; Alexander, James N; Bell, Bruce M; Dunkle, Melissa N

    2016-04-01

    Electrospray ionization (ESI) of solution mixtures often generates complex mass spectra, even following liquid chromatography (LC), due to analyte multiple charging. Multiple charge state distributions can lead to isobaric interferences, mass spectral congestion, and ambiguous ion identification. As a consequence, data interpretation increases in complexity. Several charge reduction mass spectrometry (MS) approaches have been previously developed to reduce the average charge state of gaseous ions; however, all of these techniques have been restricted to direct infusion MS. In this study, synthetic polyols and surfactants separated by liquid chromatography and ionized by positive mode ESI have been subjected to polonium-210 α-particle radiation to reduce the average charge state to singly charged cations prior to mass analysis. LC/MS analysis of 5000 molecular weight poly(ethylene glycol) (PEG5000) generated an average charge state of 5.88+; whereupon, liquid chromatography/electrospray ionization/charge reduction/mass spectrometry (LC/CR/MS) analysis of PEG 5000 generated an average charge state of 1.00+. The PEG5000 results demonstrated a decrease in spectral complexity and enabled facile interpretation. Other complex solution mixtures representing specific MS challenges (i.e., competitive ionization and isobaric ion overlap) were explored and analyzed with LC/CR/MS to demonstrate the benefits of coupling LC to CR/MS. For example, polyol information related to initiator, identity/relative amount of monomer, and estimated molecular weight was characterized in random and triblock ethylene oxide/propylene oxide polyols using LC/CR/MS. LC/CR/MS is a new analytical technique for the analysis of complex mixtures. PMID:26971559

  8. Highly enantioselective oxidative couplings of 2-naphthols catalyzed by chiral bimetallic oxovanadium complexes with either oxygen or air as oxidant.

    PubMed

    Guo, Qi-Xiang; Wu, Zhi-Jun; Luo, Zhi-Bin; Liu, Quan-Zhong; Ye, Jian-Liang; Luo, Shi-Wei; Cun, Lin-Feng; Gong, Liu-Zhu

    2007-11-14

    The chiral bimetallic oxovanadium complexes have been designed for the enantioselective oxidative coupling of 2-naphthols bearing various substituents at C6 and/or C7. The chirality transferring from the amino acid to the axis of the biphenyl in oxovanadium complexes 2 was found to occur with the use of UV and CD spectra and DFT calculation. The homo-coupling reaction with oxygen as the oxidant was promoted by 5 mol % of an oxovanadium complex derived from L-isoleucine and achiral biphenol to afford binaphthols in nearly quantitative yields with high enantioselectivities of up to 98% ee. An oxovanadium complex derived from L-isoleucine and H8-binaphthol is highly efficient at catalyzing the air-oxidized coupling of 2-naphthols with excellent enantioselectivities of up to 97% ee. 51V NMR study shows that the oxovanadium complexes have two vanadium(V) species. Kinetic studies, the cross-coupling reaction, and HRMS spectral studies on the reaction have been carried out and illustrate that two vanadium(V) species are both involved in catalysis and that the coupling reaction undergoes a radical-radical mechanism in an intramolecular manner. Quantum mechanical calculations rationalize the importance of the cooperative effects of the axial chirality matching S-amino acids on the stereocontrol of the oxidative coupling reaction. The application of the transformation in the preparation of chiral ligands and conjugated polymers confirms the importance of the current process in organic synthesis. PMID:17956093

  9. Complex band structures of transition metal dichalcogenide monolayers with spin–orbit coupling effects

    NASA Astrophysics Data System (ADS)

    Szczęśniak, Dominik; Ennaoui, Ahmed; Ahzi, Saïd

    2016-09-01

    Recently, the transition metal dichalcogenides have attracted renewed attention due to the potential use of their low-dimensional forms in both nano- and opto-electronics. In such applications, the electronic and transport properties of monolayer transition metal dichalcogenides play a pivotal role. The present paper provides a new insight into these essential properties by studying the complex band structures of popular transition metal dichalcogenide monolayers (MX 2, where M  =  Mo, W; X  =  S, Se, Te) while including spin–orbit coupling effects. The conducted symmetry-based tight-binding calculations show that the analytical continuation from the real band structures to the complex momentum space leads to nonlinear generalized eigenvalue problems. Herein an efficient method for solving such a class of nonlinear problems is presented and yields a complete set of physically relevant eigenvalues. Solutions obtained by this method are characterized and classified into propagating and evanescent states, where the latter states manifest not only monotonic but also oscillatory decay character. It is observed that some of the oscillatory evanescent states create characteristic complex loops at the direct band gap of MX 2 monolayers, where electrons can directly tunnel between the band gap edges. To describe these tunneling currents, decay behavior of electronic states in the forbidden energy region is elucidated and their importance within the ballistic transport regime is briefly discussed.

  10. Single-molecule resolution of G protein-coupled receptor (GPCR) complexes.

    PubMed

    Jonas, Kim C; Huhtaniemi, Ilpo; Hanyaloglu, Aylin C

    2016-01-01

    The organization of G protein-coupled receptors (GPCRs) into dimers and higher-order oligomers has provided a potential mechanistic system in defining complex GPCR responses. Despite being studied for nearly 20 years it has, and still is, been an area of controversy. Although technology has developed to quantitatively measure these associations in real time, identify the structural interfaces and even systems to understand the physiological significance of di/oligomerization, key questions remain outstanding including the role of each individual complex from the monomer to the higher-order oligomer, in their native system. Recently, single-molecule microscopy approaches have provided the tools to directly visualize individual GPCRs in dimers and oligomers, though as with any technological development each have their advantages and limitations. This chapter will describe these recent developments in single-molecule fluorescent microscopy, focusing on our recent application of super-resolution imaging of the GPCR for the luteinizing hormone/chorionic gonadotropin to quantify GPCR monomers and formation of protomers in to dimers and distinct oligomeric forms. We present our approach, considerations, strategy, and challenges to visualize this receptor beyond the light diffraction limit via photoactivated localization microscopy with photoactivatable dyes. The addition of super-resolution approaches to the GPCR "nano-tool kit" will pave the way for novel avenues to answer outstanding questions regarding the existence and significance of these complexes to GPCR signaling. PMID:26928539

  11. Vortex-soliton complexes in coupled nonlinear Schrödinger equations with unequal dispersion coefficients

    NASA Astrophysics Data System (ADS)

    Charalampidis, E. G.; Kevrekidis, P. G.; Frantzeskakis, D. J.; Malomed, B. A.

    2016-08-01

    We consider a two-component, two-dimensional nonlinear Schrödinger system with unequal dispersion coefficients and self-defocusing nonlinearities, chiefly with equal strengths of the self- and cross-interactions. In this setting, a natural waveform with a nonvanishing background in one component is a vortex, which induces an effective potential well in the second component, via the nonlinear coupling of the two components. We show that the potential well may support not only the fundamental bound state, but also multiring excited radial state complexes for suitable ranges of values of the dispersion coefficient of the second component. We systematically explore the existence, stability, and nonlinear dynamics of these states. The complexes involving the excited radial states are weakly unstable, with a growth rate depending on the dispersion of the second component. Their evolution leads to transformation of the multiring complexes into stable vortex-bright solitons ones with the fundamental state in the second component. The excited states may be stabilized by a harmonic-oscillator trapping potential, as well as by unequal strengths of the self- and cross-repulsive nonlinearities.

  12. Complex band structures of transition metal dichalcogenide monolayers with spin-orbit coupling effects.

    PubMed

    Szczęśniak, Dominik; Ennaoui, Ahmed; Ahzi, Saïd

    2016-09-01

    Recently, the transition metal dichalcogenides have attracted renewed attention due to the potential use of their low-dimensional forms in both nano- and opto-electronics. In such applications, the electronic and transport properties of monolayer transition metal dichalcogenides play a pivotal role. The present paper provides a new insight into these essential properties by studying the complex band structures of popular transition metal dichalcogenide monolayers (MX 2, where M  =  Mo, W; X  =  S, Se, Te) while including spin-orbit coupling effects. The conducted symmetry-based tight-binding calculations show that the analytical continuation from the real band structures to the complex momentum space leads to nonlinear generalized eigenvalue problems. Herein an efficient method for solving such a class of nonlinear problems is presented and yields a complete set of physically relevant eigenvalues. Solutions obtained by this method are characterized and classified into propagating and evanescent states, where the latter states manifest not only monotonic but also oscillatory decay character. It is observed that some of the oscillatory evanescent states create characteristic complex loops at the direct band gap of MX 2 monolayers, where electrons can directly tunnel between the band gap edges. To describe these tunneling currents, decay behavior of electronic states in the forbidden energy region is elucidated and their importance within the ballistic transport regime is briefly discussed. PMID:27367475

  13. A self-consistent three-wave coupling model with complex linear frequencies

    SciTech Connect

    Kim, J.-H.; Terry, P. W.

    2011-09-15

    A three-wave coupling model with complex linear frequencies is investigated for the nonlinear interaction in a triad that has linearly unstable and stable modes. Time scales associated with linear and nonlinear physics are identified and compared with features of the frequency spectrum. From appropriate time scales, the frequency spectra are well characterized even in the transition to the steady state. The nonlinear time scales that best match spectral features are the nonlinear frequency of the fixed point and a frequency that depends on the amplitude displacement from the fixed point through the large-amplitude Jacobian elliptic solution. Two limited efforts to model the effect of other triads suggest robustness in the single triad results.

  14. Magnetic Field Induced Shear Flow in a Strongly Coupled Complex Plasma

    NASA Astrophysics Data System (ADS)

    Bandyopadhyay, P.; Konopka, U.; Jiang, K.; Morfill, G.

    2011-11-01

    We address an experimental observation of shear flow of micron sized dust particles in a strongly coupled complex plasma in presence of a homogeneous magnetic field. Two concentric Aluminum rings of different size are placed on the lower electrode of a radio frequency (rf) parallel plate discharge. The modified local sheath electric field is pointing outward/inward close to the inner/outher ring, respectively. The microparticles, confined by the rings and subject to an ion wind that driven by the local sheath electric field and deflected by an externally applied magnetic field, start flowing in azimuthal direction. Depending upon the rf amplitudes on the electrodes, the dust layers show rotation in opposite direction at the edges of the ring-shaped cloud resulting a strong shear in its center. MD simulations shows a good agreement with the experimental results.

  15. Coupled ice shelf-ocean modeling and complex grounding line retreat from a seabed ridge

    NASA Astrophysics Data System (ADS)

    De Rydt, J.; Gudmundsson, G. H.

    2016-05-01

    Recent observations and modeling work have shown a complex mechanical coupling between Antarctica's floating ice shelves and the adjacent grounded ice sheet. A prime example is Pine Island Glacier, West Antarctica, which has a strong negative mass balance caused by a recent increase in ocean-induced melting of its ice shelf. The mass loss coincides with the retreat of the grounding line from a seabed ridge, on which it was at least partly grounded until the 1970s. At present, it is unclear what has caused the onset of this retreat and how feedback mechanisms between the ocean and ice shelf geometry have influenced the ice dynamics. To address these questions, we present the first results from an offline coupling between a state-of-the-art shallow-ice flow model with grounding line resolving capabilities and a three-dimensional ocean general circulation model with a static implementation of the ice shelf. A series of idealized experiments simulate the retreat from a seabed ridge in response to changes in the ocean forcing, and we show that the retreat becomes irreversible after 20 years of warm ocean conditions. A comparison to experiments with a simple depth-dependent melt rate parameterization demonstrates that such parameterizations are unable to capture the details of the retreat process, and they overestimate mass loss by more than 40% over a 50 year timescale.

  16. Impact of asymptomatic infection on coupled disease-behavior dynamics in complex networks

    NASA Astrophysics Data System (ADS)

    Zhang, Hai-Feng; Xie, Jia-Rong; Chen, Han-Shuang; Liu, Can; Small, Michael

    2016-05-01

    Studies on how to model the interplay between diseases and behavioral responses (so-called coupled disease-behavior interaction) have attracted increasing attention. Owing to the lack of obvious clinical evidence of diseases, or the incomplete information related to the disease, the risks of infection cannot be perceived and may lead to inappropriate behavioral responses. Therefore, how to quantitatively analyze the impacts of asymptomatic infection on the interplay between diseases and behavioral responses is of particular importance. In this letter, under the complex network framework, we study the coupled disease-behavior interaction model by dividing infectious individuals into two states: U-state (without evident clinical symptoms, labelled as U) and I-state (with evident clinical symptoms, labelled as I). A susceptible individual can be infected by U- or I-nodes, however, since the U-nodes cannot be easily observed, susceptible individuals take behavioral responses only when they contact I-nodes. The mechanism is considered in the improved Susceptible-Infected-Susceptible (SIS) model and the improved Susceptible-Infected-Recovered (SIR) model, respectively. Then, one of the most concerned problems in spreading dynamics: the epidemic thresholds for the two models are given by two methods. The analytic results quantitatively describe the influence of different factors, such as asymptomatic infection, the awareness rate, the network structure, and so forth, on the epidemic thresholds. Moreover, because of the irreversible process of the SIR model, the suppression effect of the improved SIR model is weaker than the improved SIS model.

  17. A Tractable Method for Describing Complex Couplings between Neurons and Population Rate.

    PubMed

    Gardella, Christophe; Marre, Olivier; Mora, Thierry

    2016-01-01

    Neurons within a population are strongly correlated, but how to simply capture these correlations is still a matter of debate. Recent studies have shown that the activity of each cell is influenced by the population rate, defined as the summed activity of all neurons in the population. However, an explicit, tractable model for these interactions is still lacking. Here we build a probabilistic model of population activity that reproduces the firing rate of each cell, the distribution of the population rate, and the linear coupling between them. This model is tractable, meaning that its parameters can be learned in a few seconds on a standard computer even for large population recordings. We inferred our model for a population of 160 neurons in the salamander retina. In this population, single-cell firing rates depended in unexpected ways on the population rate. In particular, some cells had a preferred population rate at which they were most likely to fire. These complex dependencies could not be explained by a linear coupling between the cell and the population rate. We designed a more general, still tractable model that could fully account for these nonlinear dependencies. We thus provide a simple and computationally tractable way to learn models that reproduce the dependence of each neuron on the population rate. PMID:27570827

  18. Coupled ice shelf-ocean modeling and complex grounding line retreat for Pine Island Glacier

    NASA Astrophysics Data System (ADS)

    De Rydt, Jan; Gudmundsson, Hilmar

    2016-04-01

    Recent observations and modeling work have shown a complex mechanical coupling between Antarctica's floating ice shelves and the adjacent grounded ice sheet. A prime example is Pine Island Glacier, West Antarctica, which has a strong negative mass balance caused by a recent increase in ocean-induced melting of its ice shelf. The mass loss coincides with the retreat of the grounding line from a seabed ridge, on which it was at least partly grounded until the 1970s. At present, it is unclear what has caused the onset of this retreat, and how feedback mechanisms between the ocean and iceshelf geometry have influenced the ice dynamics. To address these questions, we present results from an offline coupling between a state-of-the-art shallow-ice flow model with grounding line resolving capabilities, and a three-dimensional ocean general circulation model with a static implementation of the ice shelf. A series of idealized experiments simulate the retreat from a seabed ridge in response to changes in the ocean forcing, and we show that the retreat becomes irreversible after 20 years of warm ocean conditions. A comparison to experiments with a simple depth-dependent meltrate parameterisation demonstrates that such parameterizations are unable to capture the details of the retreat process, and they overestimate mass loss by more than 40% over a 50-year timescale.

  19. A Tractable Method for Describing Complex Couplings between Neurons and Population Rate

    PubMed Central

    Marre, Olivier

    2016-01-01

    Abstract Neurons within a population are strongly correlated, but how to simply capture these correlations is still a matter of debate. Recent studies have shown that the activity of each cell is influenced by the population rate, defined as the summed activity of all neurons in the population. However, an explicit, tractable model for these interactions is still lacking. Here we build a probabilistic model of population activity that reproduces the firing rate of each cell, the distribution of the population rate, and the linear coupling between them. This model is tractable, meaning that its parameters can be learned in a few seconds on a standard computer even for large population recordings. We inferred our model for a population of 160 neurons in the salamander retina. In this population, single-cell firing rates depended in unexpected ways on the population rate. In particular, some cells had a preferred population rate at which they were most likely to fire. These complex dependencies could not be explained by a linear coupling between the cell and the population rate. We designed a more general, still tractable model that could fully account for these nonlinear dependencies. We thus provide a simple and computationally tractable way to learn models that reproduce the dependence of each neuron on the population rate. PMID:27570827

  20. Soliton interactions and complexes for coupled nonlinear Schrödinger equations.

    PubMed

    Jiang, Yan; Tian, Bo; Liu, Wen-Jun; Sun, Kun; Li, Min; Wang, Pan

    2012-03-01

    Under investigation in this paper are the coupled nonlinear Schrödinger (CNLS) equations, which can be used to govern the optical-soliton propagation and interaction in such optical media as the multimode fibers, fiber arrays, and birefringent fibers. By taking the 3-CNLS equations as an example for the N-CNLS ones (N≥3), we derive the analytic mixed-type two- and three-soliton solutions in more general forms than those obtained in the previous studies with the Hirota method and symbolic computation. With the choice of parameters for those soliton solutions, soliton interactions and complexes are investigated through the asymptotic and graphic analysis. Soliton interactions and complexes with the bound dark solitons in a mode or two modes are observed, including that (i) the two bright solitons display the breatherlike structures while the two dark ones stay parallel, (ii) the two bright and dark solitons all stay parallel, and (iii) the states of the bound solitons change from the breatherlike structures to the parallel one even with the distance between those solitons smaller than that before the interaction with the regular one soliton. Asymptotic analysis is also used to investigate the elastic and inelastic interactions between the bound solitons and the regular one soliton. Furthermore, some discussions are extended to the N-CNLS equations (N>3). Our results might be helpful in such applications as the soliton switch, optical computing, and soliton amplification in the nonlinear optics. PMID:22587200

  1. Hsp40 Couples with the CSPα Chaperone Complex upon Induction of the Heat Shock Response

    PubMed Central

    Gibbs, Sarah J.; Barren, Brandy; Beck, Katy E.; Proft, Juliane; Zhao, Xiaoxi; Noskova, Tatiana; Braun, Andrew P.; Artemyev, Nikolai O.; Braun, Janice E. A.

    2009-01-01

    In response to a conditioning stress, the expression of a set of molecular chaperones called heat shock proteins is increased. In neurons, stress-induced and constitutively expressed molecular chaperones protect against damage induced by ischemia and neurodegenerative diseases, however the molecular basis of this protection is not known. Here we have investigated the crosstalk between stress-induced chaperones and cysteine string protein (CSPα). CSPα is a constitutively expressed synaptic vesicle protein bearing a J domain and a cysteine rich “string” region that has been implicated in the long term functional integrity of synaptic transmission and the defense against neurodegeneration. We have shown previously that the CSPα chaperone complex increases isoproterenol-mediated signaling by stimulating GDP/GTP exchange of Gαs. In this report we demonstrate that in response to heat shock or treatment with the Hsp90 inhibitor geldanamycin, the J protein Hsp40 becomes a major component of the CSPα complex. Association of Hsp40 with CSPα decreases CSPα-CSPα dimerization and enhances the CSPα-induced increase in steady state GTP hydrolysis of Gαs. This newly identified CSPα-Hsp40 association reveals a previously undescribed coupling of J proteins. In view of the crucial importance of stress-induced chaperones in the protection against cell death, our data attribute a role for Hsp40 crosstalk with CSPα in neuroprotection. PMID:19242542

  2. Modular Approaches to Diversified Soft Lewis Basic Complexants through Suzuki-Miyaura Cross-Coupling of Bromoheteroarenes with Organotrifluoroborates.

    PubMed

    Chin, Ai Lin; Carrick, Jesse D

    2016-02-01

    Remediation or transmutation of spent nuclear fuel obtained as a function of energy production and legacy waste remains a significant environmental concern. Substantive efforts over the last three decades have focused on the potential of soft-Lewis basic complexants for the chemoselective separation of trivalent actinides from lanthanides in biphasic solvent systems. Recent efforts in this laboratory have focused on the concept of modularity to rapidly prepare complexants and complexant scaffolds not easily accessible via traditional linear methods in a convergent manner to better understand solubility and complexation structure/activity function in process-relevant solvents. The current work describes an efficient method for the construction of diversified complexants through multi-Suzuki-Miyaura cross-coupling of bromoheteroarenes with organotrifluoroborates affording efficient access to 22 novel materials in 43-99% yield over two, three, or four cross-couplings on the same scaffold. Optimization of the catalyst/ligand system, application, and limitations are reported herein. PMID:26751755

  3. Reductive Coupling of Nitrogen Monoxide (•NO) Facilitated by Heme/Copper Complexes

    PubMed Central

    Wang, Jun; Schopfer, Mark P.; Puiu, Simona C.; Sarjeant, Amy A. N.; Karlin, Kenneth D.

    2009-01-01

    The interactions of nitrogen monoxide (•NO; nitric oxide) with transition metal centers continue to be of great interest, in part due to their importance in biochemical processes. Here, we describe •NO(g) reductive coupling chemistry of possible relevance to that process (i.e., nitric oxide reductase (NOR) biochemistry) which occurs at the heme/Cu active site of cytochrome c oxidases (CcOs). In this report, heme/Cu/•NO(g) activity is studied using 1:1 ratios of heme and copper complex components, (F8)Fe (F8 = tetrakis(2,6-difluorophenyl)porphyrinate(2-)) and [(tmpa)CuI(MeCN)]+ (TMPA = tris(2-pyridylmethyl)amine). The starting point for heme chemistry is the mononitrosyl complex (F8)Fe(NO) (λmax = 399 (Soret), 541 nm in acetone). Variable temperature 1H- and 2H-NMR spectra reveal a broad peak at δ = 6.05 ppm (pyrrole) at RT, which gives rise to asymmetrically split pyrrole peaks at 9.12 and 8.54 ppm at −80°C. A new heme dinitrosyl species, (F8)Fe(NO)2, obtained by bubbling (F8)Fe(NO) with •NO(g) at −80 °C, could be reversibly formed, as monitored by UV-vis (λmax = 426 (Soret), 538 nm in acetone), EPR (silent), and NMR spectroscopies, i.e. the mono-NO complex was regenerated upon warming to RT. (F8)Fe(NO)2 reacts with [(tmpa)CuI(MeCN)]+ and two equiv of acid to give [(F8)FeIII]+, [(tmpa)CuII(solvent)]2+ and N2O(g), fitting the stoichiometric •NO(g) reductive coupling reaction: 2 •NO(g) + FeII + CuI + 2 H+ → N2O(g) + FeIII + CuII + H2O, equivalent to one enzyme turnover. Control reaction chemistry shows that both iron and copper centers are required for the NOR type chemistry observed, and that if acid is not present, half the •NO is trapped as a (F8)Fe(NO) complex, while the remaining nitrogen monoxide undergoes copper complex promoted disproportionation chemistry. As part of this study, [(F8)FeIII]SbF6 was synthesized and characterized by X-ray crystallography, along with EPR (77 K: g = 5.84 and 6.12 in CH2Cl2 and THF, respectively) and

  4. Ab initio density matrix renormalization group study of magnetic coupling in dinuclear iron and chromium complexes

    SciTech Connect

    Harris, Travis V.; Morokuma, Keiji; Kurashige, Yuki; Yanai, Takeshi

    2014-02-07

    The applicability of ab initio multireference wavefunction-based methods to the study of magnetic complexes has been restricted by the quickly rising active-space requirements of oligonuclear systems and dinuclear complexes with S > 1 spin centers. Ab initio density matrix renormalization group (DMRG) methods built upon an efficient parameterization of the correlation network enable the use of much larger active spaces, and therefore may offer a way forward. Here, we apply DMRG-CASSCF to the dinuclear complexes [Fe{sub 2}OCl{sub 6}]{sup 2−} and [Cr{sub 2}O(NH{sub 3}){sub 10}]{sup 4+}. After developing the methodology through systematic basis set and DMRG M testing, we explore the effects of extended active spaces that are beyond the limit of conventional methods. We find that DMRG-CASSCF with active spaces including the metal d orbitals, occupied bridging-ligand orbitals, and their virtual double shells already capture a major portion of the dynamic correlation effects, accurately reproducing the experimental magnetic coupling constant (J) of [Fe{sub 2}OCl{sub 6}]{sup 2−} with (16e,26o), and considerably improving the smaller active space results for [Cr{sub 2}O(NH{sub 3}){sub 10}]{sup 4+} with (12e,32o). For comparison, we perform conventional MRCI+Q calculations and find the J values to be consistent with those from DMRG-CASSCF. In contrast to previous studies, the higher spin states of the two systems show similar deviations from the Heisenberg spectrum, regardless of the computational method.

  5. Plexciton Dynamics: Exciton-Plasmon Coupling in a J-Aggregate-Au Nanoshell Complex Provides a Mechanism for Nonlinearity

    SciTech Connect

    Fofang, Nche T.; Grady, Nathaniel K.; Fan, Zhiyuan; Govorov, Alexander; Halas, Naomi J.

    2011-03-18

    Coherently coupled plasmons and excitons give rise to new optical excitations- plexcitons - due to the strong coupling of these two oscillator systems. Time-resolved studies of J-aggregate-Au nanoshell complexes when the nanoshell plasmon and J-aggregate exciton energies are degenerate probe the dynamical behavior of this coupled system. Transient absorption of the interacting plasmon-exciton system is observed, in dramatic contrast to the photoinduced transmission of the pristine J-aggregate. An additional, transient Fano-shaped modulation within the Fano dip is also observable. The behavior of the J-aggregate-Au nanoshell complex is described by a combined one-exciton and two-exciton state model coupled to the nanoshell plasmon.

  6. Tetracoordinated Bis-phenanthroline Copper-Complex Couple as Efficient Redox Mediators for Dye Solar Cells.

    PubMed

    Magni, Mirko; Giannuzzi, Roberto; Colombo, Alessia; Cipolla, Maria Pia; Dragonetti, Claudia; Caramori, Stefano; Carli, Stefano; Grisorio, Roberto; Suranna, Gian Paolo; Bignozzi, Carlo Alberto; Roberto, Dominique; Manca, Michele

    2016-06-01

    A tetracoordinated redox couple, made by [Cu(2-mesityl-4,7-dimethyl-1,10-phenanthroline)2][PF6], 1, and its Cu(II) form [Cu(2-mesityl-4,7-dimethyl-1,10-phenanthroline)2][PF6]2, 2, has been synthesized, and its electrochemical and photochemical features have been investigated and compared with those of a previously published Cu(2+)/Cu(+) redox shuttle, namely, [Cu(2,9-dimethyl-1,10-phenanthroline)2][PF6], 3, and its pentacoordinated oxidized form [Cu(2,9-dimethyl-1,10-phenanthroline)2Cl][PF6], 4. The detrimental effect of the fifth Cl(-) ancillary ligand on the charge transfer kinetics of the redox shuttles has been exhaustively demonstrated. Appropriately balanced Cu-based electrolytes have been then formulated and tested in dye solar cells in combination with a π-extended benzothiadiazole dye. The bis-phenanthroline Cu-complexes, 1 and 2, have been found to provide an overall 4.4% solar energy conversion efficiency, which is more than twice that of the literature benchmark couple, 3 and 4, employing a Cl-coordinated oxidized species and even comparable with the performances of a I(-)/I3(-) electrolyte of analogous concentration. A fast counter-electrode reaction, due to the excellent electrochemical reversibility of 2, and a high electron collection efficiency, allowed through the efficient dye regeneration kinetics exerted by 1, represents two major characteristics of these copper-based electron mediators and may constitute a pivotal step toward the development of a next generation of copper-based efficient iodine-free redox shuttles. PMID:27212146

  7. Dynamic coupling of complex brain networks and dual-task behavior.

    PubMed

    Alavash, Mohsen; Thiel, Christiane M; Gießing, Carsten

    2016-04-01

    Multi-tasking is a familiar situation where behavioral performance is often challenged. To date, fMRI studies investigating the neural underpinning of dual-task interference have mostly relied on local brain activation maps or static brain connectivity networks. Here, based on task fMRI we explored how fluctuations in behavior during concurrent performance of a visuospatial and a speech task relate to alternations in the topology of dynamic brain connectivity networks. We combined a time-resolved functional connectivity and complex network analysis with a sliding window approach applied to the trial by trial behavioral responses to investigate the coupling between dynamic brain networks and dual-task behavior at close temporal proximity. Participants showed fluctuations in their dual-task behavior over time, with the accuracy in the component tasks being statistically independent from one another. On the global level of brain networks we found that dynamic changes of network topology were differentially coupled with the behavior in each component task during the course of dual-tasking. While momentary decrease in the global efficiency of dynamic brain networks correlated with subsequent increase in visuospatial accuracy, better speech performance was preceded by higher global network efficiency and was followed by an increase in between-module connectivity over time. Additionally, dynamic alternations in the modular organization of brain networks at the posterior cingulate cortex were differentially predictive for the visuospatial as compared to the speech accuracy over time. Our results provide the first evidence that, during the course of dual-tasking, each component task is supported by a distinct topological configuration of brain connectivity networks. This finding suggests that the failure of functional brain connectivity networks to adapt to an optimal topology supporting the performance in both component tasks at the same time contributes to the moment to

  8. Accurate gradient approximation for complex interface problems in 3D by an improved coupling interface method

    SciTech Connect

    Shu, Yu-Chen; Chern, I-Liang; Chang, Chien C.

    2014-10-15

    Most elliptic interface solvers become complicated for complex interface problems at those “exceptional points” where there are not enough neighboring interior points for high order interpolation. Such complication increases especially in three dimensions. Usually, the solvers are thus reduced to low order accuracy. In this paper, we classify these exceptional points and propose two recipes to maintain order of accuracy there, aiming at improving the previous coupling interface method [26]. Yet the idea is also applicable to other interface solvers. The main idea is to have at least first order approximations for second order derivatives at those exceptional points. Recipe 1 is to use the finite difference approximation for the second order derivatives at a nearby interior grid point, whenever this is possible. Recipe 2 is to flip domain signatures and introduce a ghost state so that a second-order method can be applied. This ghost state is a smooth extension of the solution at the exceptional point from the other side of the interface. The original state is recovered by a post-processing using nearby states and jump conditions. The choice of recipes is determined by a classification scheme of the exceptional points. The method renders the solution and its gradient uniformly second-order accurate in the entire computed domain. Numerical examples are provided to illustrate the second order accuracy of the presently proposed method in approximating the gradients of the original states for some complex interfaces which we had tested previous in two and three dimensions, and a real molecule ( (1D63)) which is double-helix shape and composed of hundreds of atoms.

  9. Simplifying the complexity of a coupled carbon turnover and pesticide degradation model

    NASA Astrophysics Data System (ADS)

    Marschmann, Gianna; Erhardt, André H.; Pagel, Holger; Kügler, Philipp; Streck, Thilo

    2016-04-01

    The mechanistic one-dimensional model PECCAD (PEsticide degradation Coupled to CArbon turnover in the Detritusphere; Pagel et al. 2014, Biogeochemistry 117, 185-204) has been developed as a tool to elucidate regulation mechanisms of pesticide degradation in soil. A feature of this model is that it integrates functional traits of microorganisms, identifiable by molecular tools, and physicochemical processes such as transport and sorption that control substrate availability. Predicting the behavior of microbially active interfaces demands a fundamental understanding of factors controlling their dynamics. Concepts from dynamical systems theory allow us to study general properties of the model such as its qualitative behavior, intrinsic timescales and dynamic stability: Using a Latin hypercube method we sampled the parameter space for physically realistic steady states of the PECCAD ODE system and set up a numerical continuation and bifurcation problem with the open-source toolbox MatCont in order to obtain a complete classification of the dynamical system's behaviour. Bifurcation analysis reveals an equilibrium state of the system entirely controlled by fungal kinetic parameters. The equilibrium is generally unstable in response to small perturbations except for a small band in parameter space where the pesticide pool is stable. Time scale separation is a phenomenon that occurs in almost every complex open physical system. Motivated by the notion of "initial-stage" and "late-stage" decomposers and the concept of r-, K- or L-selected microbial life strategies, we test the applicability of geometric singular perturbation theory to identify fast and slow time scales of PECCAD. Revealing a generic fast-slow structure would greatly simplify the analysis of complex models of organic matter turnover by reducing the number of unknowns and parameters and providing a systematic mathematical framework for studying their properties.

  10. Accurate gradient approximation for complex interface problems in 3D by an improved coupling interface method

    NASA Astrophysics Data System (ADS)

    Shu, Yu-Chen; Chern, I.-Liang; Chang, Chien C.

    2014-10-01

    Most elliptic interface solvers become complicated for complex interface problems at those “exceptional points” where there are not enough neighboring interior points for high order interpolation. Such complication increases especially in three dimensions. Usually, the solvers are thus reduced to low order accuracy. In this paper, we classify these exceptional points and propose two recipes to maintain order of accuracy there, aiming at improving the previous coupling interface method [26]. Yet the idea is also applicable to other interface solvers. The main idea is to have at least first order approximations for second order derivatives at those exceptional points. Recipe 1 is to use the finite difference approximation for the second order derivatives at a nearby interior grid point, whenever this is possible. Recipe 2 is to flip domain signatures and introduce a ghost state so that a second-order method can be applied. This ghost state is a smooth extension of the solution at the exceptional point from the other side of the interface. The original state is recovered by a post-processing using nearby states and jump conditions. The choice of recipes is determined by a classification scheme of the exceptional points. The method renders the solution and its gradient uniformly second-order accurate in the entire computed domain. Numerical examples are provided to illustrate the second order accuracy of the presently proposed method in approximating the gradients of the original states for some complex interfaces which we had tested previous in two and three dimensions, and a real molecule (1D63) which is double-helix shape and composed of hundreds of atoms.

  11. Strongly coupled binuclear uranium-oxo complexes from uranyl oxo rearrangement and reductive silylation

    NASA Astrophysics Data System (ADS)

    Arnold, Polly L.; Jones, Guy M.; Odoh, Samuel O.; Schreckenbach, Georg; Magnani, Nicola; Love, Jason B.

    2012-03-01

    The most common motif in uranium chemistry is the d0f0 uranyl ion [UO2]2+ in which the oxo groups are rigorously linear and inert. Alternative geometries, such as the cis-uranyl, have been identified theoretically and implicated in oxo-atom transfer reactions that are relevant to environmental speciation and nuclear waste remediation. Single electron reduction is now known to impart greater oxo-group reactivity, but with retention of the linear OUO motif, and reactions of the oxo groups to form new covalent bonds remain rare. Here, we describe the synthesis, structure, reactivity and magnetic properties of a binuclear uranium-oxo complex. Formed through a combination of reduction and oxo-silylation and migration from a trans to a cis position, the new butterfly-shaped Si-OUO2UO-Si molecule shows remarkably strong UV-UV coupling and chemical inertness, suggesting that this rearranged uranium oxo motif might exist for other actinide species in the environment, and have relevance to the aggregation of actinide oxide clusters.

  12. Strongly coupled binuclear uranium-oxo complexes from uranyl oxo rearrangement and reductive silylation.

    PubMed

    Arnold, Polly L; Jones, Guy M; Odoh, Samuel O; Schreckenbach, Georg; Magnani, Nicola; Love, Jason B

    2012-03-01

    The most common motif in uranium chemistry is the d(0)f(0) uranyl ion [UO(2)](2+) in which the oxo groups are rigorously linear and inert. Alternative geometries, such as the cis-uranyl, have been identified theoretically and implicated in oxo-atom transfer reactions that are relevant to environmental speciation and nuclear waste remediation. Single electron reduction is now known to impart greater oxo-group reactivity, but with retention of the linear OUO motif, and reactions of the oxo groups to form new covalent bonds remain rare. Here, we describe the synthesis, structure, reactivity and magnetic properties of a binuclear uranium-oxo complex. Formed through a combination of reduction and oxo-silylation and migration from a trans to a cis position, the new butterfly-shaped Si-OUO(2)UO-Si molecule shows remarkably strong U(V)-U(V) coupling and chemical inertness, suggesting that this rearranged uranium oxo motif might exist for other actinide species in the environment, and have relevance to the aggregation of actinide oxide clusters. PMID:22354437

  13. Communication: A reduced-space algorithm for the solution of the complex linear response equations used in coupled cluster damped response theory

    NASA Astrophysics Data System (ADS)

    Kauczor, Joanna; Norman, Patrick; Christiansen, Ove; Coriani, Sonia

    2013-12-01

    We present a reduced-space algorithm for solving the complex (damped) linear response equations required to compute the complex linear response function for the hierarchy of methods: coupled cluster singles, coupled cluster singles and iterative approximate doubles, and coupled cluster singles and doubles. The solver is the keystone element for the development of damped coupled cluster response methods for linear and nonlinear effects in resonant frequency regions.

  14. Complex image method for RF antenna-plasma inductive coupling calculation in planar geometry. Part I: basic concepts

    NASA Astrophysics Data System (ADS)

    Howling, A. A.; Guittienne, Ph; Jacquier, R.; Furno, I.

    2015-12-01

    The coupling between an inductive source and the plasma determines the power transfer efficiency and the reflected impedance in the primary circuit. Usually, the plasma coupling is analysed by means of a transformer equivalent circuit, where the plasma inductance and resistance are estimated using a global plasma model. This paper shows that, for planar RF antennas, the mutual inductance between the plasma and the primary circuit can be calculated using partial inductances and the complex image method, where the plasma coupling is determined in terms of the plasma skin depth and the distance to the plasma. To introduce the basic concepts, the mutual inductance is calculated here for a linear conductor parallel to the plasma surface. In the accompanying paper part II Guittienne et al (2015 Plasma Sources Sci. Technol. 24 065015), impedance measurements on a RF resonant planar plasma source are modeled using an impedance matrix where the plasma-antenna mutual impedances are calculated using the complex image method presented here.

  15. Active site coupling in PDE:PKA complexes promotes resetting of mammalian cAMP signaling.

    PubMed

    Krishnamurthy, Srinath; Moorthy, Balakrishnan Shenbaga; Xin Xiang, Lim; Xin Shan, Lim; Bharatham, Kavitha; Tulsian, Nikhil Kumar; Mihalek, Ivana; Anand, Ganesh S

    2014-09-16

    Cyclic 3'5' adenosine monophosphate (cAMP)-dependent-protein kinase (PKA) signaling is a fundamental regulatory pathway for mediating cellular responses to hormonal stimuli. The pathway is activated by high-affinity association of cAMP with the regulatory subunit of PKA and signal termination is achieved upon cAMP dissociation from PKA. Although steps in the activation phase are well understood, little is known on how signal termination/resetting occurs. Due to the high affinity of cAMP to PKA (KD ∼ low nM), bound cAMP does not readily dissociate from PKA, thus begging the question of how tightly bound cAMP is released from PKA to reset its signaling state to respond to subsequent stimuli. It has been recently shown that phosphodiesterases (PDEs) can catalyze dissociation of bound cAMP and thereby play an active role in cAMP signal desensitization/termination. This is achieved through direct interactions with the regulatory subunit of PKA, thereby facilitating cAMP dissociation and hydrolysis. In this study, we have mapped direct interactions between a specific cyclic nucleotide phosphodiesterase (PDE8A) and a PKA regulatory subunit (RIα isoform) in mammalian cAMP signaling, by a combination of amide hydrogen/deuterium exchange mass spectrometry, peptide array, and computational docking. The interaction interface of the PDE8A:RIα complex, probed by peptide array and hydrogen/deuterium exchange mass spectrometry, brings together regions spanning the phosphodiesterase active site and cAMP-binding sites of RIα. Computational docking combined with amide hydrogen/deuterium exchange mass spectrometry provided a model for parallel dissociation of bound cAMP from the two tandem cAMP-binding domains of RIα. Active site coupling suggests a role for substrate channeling in the PDE-dependent dissociation and hydrolysis of cAMP bound to PKA. This is the first instance, to our knowledge, of PDEs directly interacting with a cAMP-receptor protein in a mammalian system, and

  16. Spatial coupled disease-behavior framework as a dynamic and adaptive system. Reply to comments on "Coupled disease-behavior dynamics on complex networks: A review"

    NASA Astrophysics Data System (ADS)

    Wang, Zhen; Andrews, Michael A.; Wu, Zhi-Xi; Wang, Lin; Bauch, Chris T.

    2015-12-01

    We would like to begin this response by recognizing all the insightful and thought-provoking comments to our review "Coupled disease-behavior dynamics on complex networks" [1]. We find that, with their diverse expertise, all the commentators enrich the discussion on this topic, and also identify important, interesting questions [2-13], indicating how much space there still is for the development of the field. To give the readers a systematic understanding, these opinions and suggestions are roughly divided into two classes: (i) whether the coupled models could be closer to realistic observations, yet simpler [2-5,7-10,13]; and (ii) whether the hypothesis of network models could mimic the empirical networks more accurately [5-8,10-13].

  17. Complex eigensolutions of coupled flexural and longitudinal modes in a beam with inclined elastic supports with non-proportional damping

    NASA Astrophysics Data System (ADS)

    Noll, Scott; Dreyer, Jason; Singh, Rajendra

    2014-02-01

    Structure borne vibration and noise in an automobile are often explained by representing the full vehicle as a system of elastically coupled beam structures representing the body, engine cradle and body subframe where the engine is often connected to the chassis via inclined viscoelastic supports. To understand more clearly the interactions between a beam structure and isolators, this article examines the flexural and longitudinal motions in an elastic beam with intentionally inclined mounts (viscoelastic end supports). A new analytical solution is derived for the boundary coupled Euler beam and wave equations resulting in complex eigensolutions. This system is demonstrated to be self-adjoint when the support stiffness matrices are symmetric; thus, the modal analysis is used to decouple the equations of motion and solve for the steady state, damped harmonic response. Experimental validation and computational verifications confirm the validity of the proposed formulation. New and interesting phenomena are presented including coupled rigid motions, modal properties for ideal angled roller boundaries, and relationships between coupling and system modal loss factors. The ideal roller boundary conditions when inclined are seen as a limiting case of coupled longitudinal and flexural motions. In particular, the coupled rigid body motions illustrate the influence of support stiffness coupling on the eigenvalues and eigenfunctions. The relative modal strain energy concept is used to distinguish the contribution of longitudinal and flexural deformation modes. Since the beam is assumed to be undamped, the system damping is derived from the viscoelastic supports. The support damping (for a given loss factor) is shown to be redistributed between the system modes due to the inclined coupling mechanisms. Finally, this article provides valuable insight by highlighting some technical issues a real-life designer faces when balancing modeling assumptions such as rigid or elastic

  18. A novel 4-aminoantipyrine-Pd(II) complex catalyzes Suzuki–Miyaura cross-coupling reactions of aryl halides

    PubMed Central

    Mendoza-Rayo, Darío; Rincón-Medina, José A; Chacón-García, Luis

    2014-01-01

    Summary A simple and efficient catalytic system based on a Pd complex of 4-aminoantipyrine, 4-AAP–Pd(II), was found to be highly active for Suzuki–Miyaura cross-coupling of aryl iodides and bromides with phenylboronic acids under mild reaction conditions. Good to excellent product yields from the cross-coupling reaction can be achieved when the reaction is carried out in ethanol, in the open air, using low loading of 4-AAP–Pd(II) as a precatalyst, and in the presence of aqueous K2CO3 as the base. A variety of functional groups are tolerated. PMID:25550748

  19. Amide Coupling Reaction for the Synthesis of Bispyridine-based Ligands and Their Complexation to Platinum as Dinuclear Anticancer Agents

    PubMed Central

    Apps, Michael G.; Johnson, Ben W.; Sutcliffe, Oliver B.; Brown, Sarah D.; Wheate, Nial J.

    2014-01-01

    Amide coupling reactions can be used to synthesize bispyridine-based ligands for use as bridging linkers in multinuclear platinum anticancer drugs. Isonicotinic acid, or its derivatives, are coupled to variable length diaminoalkane chains under an inert atmosphere in anhydrous DMF or DMSO with the use of a weak base, triethylamine, and a coupling agent, 1-propylphosphonic anhydride. The products precipitate from solution upon formation or can be precipitated by the addition of water. If desired, the ligands can be further purified by recrystallization from hot water. Dinuclear platinum complex synthesis using the bispyridine ligands is done in hot water using transplatin. The most informative of the chemical characterization techniques to determine the structure and gross purity of both the bispyridine ligands and the final platinum complexes is 1H NMR with particular analysis of the aromatic region of the spectra (7-9 ppm). The platinum complexes have potential application as anticancer agents and the synthesis method can be modified to produce trinuclear and other multinuclear complexes with different hydrogen bonding functionality in the bridging ligand. PMID:24893964

  20. Assessment of the CCSD and CCSD(T) Coupled-Cluster Methods in Calculating Heats of Formation for Zn Complexes

    NASA Astrophysics Data System (ADS)

    Weaver, Michael N.; Yang, Yue; Merz, Kenneth M.

    2009-08-01

    Heats of formation were calculated using coupled-cluster methods for a series of zinc complexes. The calculated values were evaluated against previously conducted computational studies using density functional methods as well as experimental values. Heats of formation for nine neutral ZnXn complexes [X = -Zn, -H, -O, -F2, -S, -Cl, -Cl2, -CH3, (-CH3)2] were determined at the CCSD and CCSD(T) levels using the 6-31G** and TZVP basis sets as well as the LANL2DZ-6-31G** (LACVP**) and LANL2DZ-TZVP hybrid basis sets. The CCSD(T)/6-31G** level of theory was found to predict the heat of formation for the nonalkyl Zn complexes most accurately. The alkyl Zn species were problematic in that none of the methods that were tested accurately predicted the heat of formation for these complexes. In instances where experimental geometric parameters were available, these were most accurately predicted by the CCSD/6-31G** level of theory; going to CCSD(T) did not improve agreement with the experimental values. Coupled-cluster methods did not offer a systemic improvement over DFT calculations for a given functional/basis set combination. With the exceptions of ZnH and ZnF2, there are multiple density functionals that outperform coupled-cluster calculations with the 6-31G** basis set.

  1. Exciton-Phonon Interaction Effects in II-Vi Compound Semiconductor Quantum Wells

    NASA Astrophysics Data System (ADS)

    Pelekanos, Nikolaos Themelis

    1992-01-01

    In this thesis, we report on two specific examples of exciton-LO phonon Frohlich interaction effects, namely, hot carrier relaxation and temperature dependent exciton linewidth broadening. These phenomena are considered in the context of quasi-two dimensional excitons in strongly polar II-VI semiconductor quantum wells. Hot-exciton luminescence phenomena are investigated in a single quantum well of ZnTe/MnTe where tunneling through thin MnTe barrier layers suppresses the formation of thermalized luminescence. For near resonant photoexcitation, the secondary emission spectrum is modulated by distinct LO-phonon peaks, which, for sufficiently high order of scattering ( >=4), behave like hot luminescence (HPL) as opposed to resonant Raman scattering. This is confirmed by time-resolved spectroscopy as well as by steady-state characteristics such as linewidth broadening and lack of polarization memory. Several novel observations are made: (1) The LO-phonon intermediated energy relaxation involves Coulomb-correlated pairs, i.e. hot excitons, as opposed to independently-relaxing free electrons and holes. (2) The additional weak disorder originating from QW thickness fluctuations plays a major role in the details of the HPL spectra. The major contribution to the ground state exciton linewidth at room temperature originates from LO phonon -intermediated exciton scattering to higher exciton states. A measure of the effect is given by the parameter Gamma_{LO} which increases with the polarity of the material and is independent of dimensionality provided that the LO phonon energy is greater than the exciton binding energy. Measurements of Gamma_{LO} are performed in two quantum well systems: CdTe/MnTe and (Zn,Cd)Se/ZnSe. In the latter system, a strong reduction of Gamma _{LO} is observed as the quantum well width becomes comparable to the three-dimensional exciton Bohr radius. This is explained in terms of a model where quasi-2D confinement effects increase the exciton binding energy to a value greater than the LO phonon energy and hence reduce the available phase space for the exciton -LO phonon scattering process. Direct confirmation of our interpretation is found in magneto-transmission experiments.

  2. Simulating Coupling Complexity in Space Plasmas: First Results from a new code

    NASA Astrophysics Data System (ADS)

    Kryukov, I.; Zank, G. P.; Pogorelov, N. V.; Raeder, J.; Ciardo, G.; Florinski, V. A.; Heerikhuisen, J.; Li, G.; Petrini, F.; Shematovich, V. I.; Winske, D.; Shaikh, D.; Webb, G. M.; Yee, H. M.

    2005-12-01

    The development of codes that embrace 'coupling complexity' via the self-consistent incorporation of multiple physical scales and multiple physical processes in models has been identified by the NRC Decadal Survey in Solar and Space Physics as a crucial necessary development in simulation/modeling technology for the coming decade. The National Science Foundation, through its Information Technology Research (ITR) Program, is supporting our efforts to develop a new class of computational code for plasmas and neutral gases that integrates multiple scales and multiple physical processes and descriptions. We are developing a highly modular, parallelized, scalable code that incorporates multiple scales by synthesizing 3 simulation technologies: 1) Computational fluid dynamics (hydrodynamics or magneto-hydrodynamics-MHD) for the large-scale plasma; 2) direct Monte Carlo simulation of atoms/neutral gas, and 3) transport code solvers to model highly energetic particle distributions. We are constructing the code so that a fourth simulation technology, hybrid simulations for microscale structures and particle distributions, can be incorporated in future work, but for the present, this aspect will be addressed at a test-particle level. This synthesis we will provide a computational tool that will advance our understanding of the physics of neutral and charged gases enormously. Besides making major advances in basic plasma physics and neutral gas problems, this project will address 3 Grand Challenge space physics problems that reflect our research interests: 1) To develop a temporal global heliospheric model which includes the interaction of solar and interstellar plasma with neutral populations (hydrogen, helium, etc., and dust), test-particle kinetic pickup ion acceleration at the termination shock, anomalous cosmic ray production, interaction with galactic cosmic rays, while incorporating the time variability of the solar wind and the solar cycle. 2) To develop a coronal

  3. Metal-metal interactions in weakly coupled mixed-valence E- and Z-diferrocenylethylene complexes.

    PubMed

    Chen, Y J; Pan, D S; Chiu, C F; Su, J X; Lin, S J; Kwan, K S

    2000-03-01

    To study metal-to-metal interactions in mixed-valence states of two weakly coupling ferrocenyl groups assembled in E or Z conformation on an ethylenic double bond, E-1,2-dimethyldiferrocenylethylene (1), Z-1,2-dimethyldi-ferrocenylethylene (2), and 1,2-diferrocenylcyclohexene (3) were synthesized and structurally characterized. Crystals of 1 are triclinic, P1, with a = 7.494(9) A, b = 10.801(3) A, c = 11.971(2) A, alpha = 102.17(2) degrees, beta = 106.12(9) degrees, gamma = 90.42(2) degrees, V = 907.8 A3, and Z = 2. Crystals of 2 are monoclinic, P2(1)/c, with a = 13.601(8) A, b = 11.104(4) A, c = 13.732(1) A, beta = 114.26(7) degrees, V = 1890.8(3) A3, and Z = 4. Crystals of 3 are orthorhombic, P2(1)2(1)2(1), with a = 5.766(2) A, b = 13.090(1) A, c = 26.695(2) A, V = 2014.9(3) A3, and Z = 4. Intervalence transition spectra (IT) and electrochemical data have been determined and compared with those of diferrocenyl-benzene (para, ortho, and meta). The comproportionation constants in nitrobenzene at 25 degrees C were found to be 490 and 813 for 1 and 3, respectively. That of 2 was not measured because of the fact that 2+ isomerizes rapidly in all solvents tested, yielding nearly a racemic mixture of E and Z conformers. This finding helps to clear the paradoxical phenomenon between experimental results of mixed-valence complexes of E- and Z-1,2-bis(1'-ethyl-1-ferrocenyl)-1,2-dimethylethylene and theories. The stability of the mixed-valence species was discussed in terms of resonance delocalization, Coulomb repulsion energy, inductive effect, magnetic interaction, structural factors, and statistical factor. According to our analysis based on the Hush formalism, the contribution due to Coulomb repulsion energy dominates the overall stability of the mixed-valence state in 1+, 2+, and 3+. Stabilization that arises from resonance delocalization is only minor and contributes less than 4% to the overall stability, even in 3+ where linked Cp rings and the ethylenic plane are

  4. Long-lived excited states of zwitterionic copper(I) complexes for photoinduced cross-dehydrogenative coupling reactions.

    PubMed

    Wang, Bin; Shelar, Deepak Prakash; Han, Xian-Zhu; Li, Ting-Ting; Guan, Xiangguo; Lu, Wei; Liu, Kun; Chen, Yong; Fu, Wen-Fu; Che, Chi-Ming

    2015-01-12

    Four heteroleptic copper(I) complexes containing phenanthroline and monoanionic nido-carborane-diphosphine ligands have been prepared and structurally characterized by various spectroscopic techniques and X-ray diffraction. These complexes exhibit intense absorptions in the visible range and excited-state lifetimes on the microsecond scale. Their application in visible-light-induced cross-dehydrogenative coupling reactions was investigated. Preliminary studies showed that one of the four copper(I) complexes is an efficient catalyst for photoinduced oxidative C-H functionalization using oxygen as oxidant. Furthermore, α-functionalized tertiary amines were obtained in good-to-excellent yields by light irradiation (λ>420 nm) of a mixture of our Cu(I) complex, tertiary amines, and a variety of nucleophiles (nitroalkane, acetone, or indoles) under aerobic conditions. Electron paramagnetic resonance measurements provided evidence for the formation of superoxide radical anions (O2(-⋅)) rather than singlet oxygen ((1)O2) during these photocatalytic reactions. PMID:25413572

  5. Effective DNA binding and cleaving tendencies of malonic acid coupled transition metal complexes

    NASA Astrophysics Data System (ADS)

    Pravin, Narayanaperumal; Utthra, Ponnukalai Ponya; Kumaravel, Ganesan; Raman, Natarajan

    2016-11-01

    Eight transition metal complexes were designed to achieve maximum biological efficacy. They were characterized by elemental analysis and various other spectroscopic techniques. The monomeric complexes were found to espouse octahedral geometry and non-electrolytic nature. The DNA interaction propensity of the complexes with calf thymus DNA (CT-DNA), studied at physiological pH by spectrophotometric, spectrofluorometric, cyclic voltammetry, and viscometric techniques revealed intercalation as the possible binding mode. Fascinatingly, the complexes were found to exhibit greater binding strength than that of the free ligands. A strong hypochromism and a slight red shift were exhibited by complex 5 among the other complexes. The intrinsic binding constant values of all the complexes compared to cisplatin reveal that they are excellent metallonucleases than that of cisplatin. The complexes were also shown to reveal displacement of the ethidium bromide, a strong intercalator using fluorescence titrations. Gel electrophoresis was used to divulge the competence of the complexes in cleaving the supercoiled pBR322 plasmid DNA. From the results, it is concluded that the complexes, especially 5, are excellent chemical nucleases in the presence of H2O2. Furthermore, the in vitro antimicrobial screening of the complexes exposes that these complexes are excellent antimicrobial agents. Overall the effect of coligands is evident from the results of all the investigations.

  6. Complexation Effect on Redox Potential of Iron(III)-Iron(II) Couple: A Simple Potentiometric Experiment

    ERIC Educational Resources Information Center

    Rizvi, Masood Ahmad; Syed, Raashid Maqsood; Khan, Badruddin

    2011-01-01

    A titration curve with multiple inflection points results when a mixture of two or more reducing agents with sufficiently different reduction potentials are titrated. In this experiment iron(II) complexes are combined into a mixture of reducing agents and are oxidized to the corresponding iron(III) complexes. As all of the complexes involve the…

  7. Broken symmetry approach to density functional calculation of magnetic anisotropy or zero field splittings for multinuclear complexes with antiferromagnetic coupling.

    PubMed

    van Wüllen, Christoph

    2009-10-29

    Antiferromagnetic coupling in multinuclear transition metal complexes usually leads to electronic ground states that cannot be described by a single Slater determinant and that are therefore difficult to describe by Kohn-Sham density functional methods. Density functional calculations in such cases are usually converged to broken symmetry solutions which break spin and, in many cases, also spatial symmetry. While a procedure exists to extract isotropic Heisenberg (exchange) coupling constants from such calculations, no such approach is yet established for the calculation of magnetic anisotropy energies or zero field splitting parameters. This work proposes such a procedure. The broken symmetry solutions are not only used to extract the exchange couplings but also single-ion D tensors which are then used to construct a (phenomenological) spin Hamiltonian, from which the magnetic anisotropy and the zero-field energy levels can be computed. The procedure is demonstrated for a bi- and a trinuclear Mn(III) model compound. PMID:19708660

  8. Superhydrophobic cotton fabric coating based on a complex layer of silica nanoparticles and perfluorooctylated quaternary ammonium silane coupling agent

    NASA Astrophysics Data System (ADS)

    Yu, Minghua; Gu, Guotuan; Meng, Wei-Dong; Qing, Feng-Ling

    2007-01-01

    A superhydrophobic complex coating for cotton fabrics based on silica nanoparticles and perfluorooctylated quaternary ammonium silane coupling agent (PFSC) was reported in this article. The complex thin film was prepared through a sol-gel process using cotton fabrics as a substrate. Silica nanoparticles in the coating made the textile surface much rougher, and perfluorooctylated quaternary ammonium silane coupling agent on the top layer of the surface lowered the surface free energy. Textiles coated with this coating showed excellent water repellent property, and water contact angle (CA) increased from 133° on cotton fabrics treated with pure PFSC without silica sol pretreatment up to 145°. The oil repellency was also improved and the contact angle of CH 2I 2 droplet on the fabric surface reached to 131°. In contrast, the contact angle of CH 2I 2 on the fabric surface treated with pure PFSC was only 125°.

  9. Endoglucanase Peripheral Loops Facilitate Complexation of Glucan Chains on Cellulose via Adaptive Coupling to the Emergent Substrate Structures

    SciTech Connect

    Lin, Yuchun; Beckham, Gregg T.; Himmel, Michael E.; Crowley, Michael F.; Chu, Jhih-wei

    2013-09-19

    We examine how the catalytic domain of a glycoside hydrolase family 7 endoglucanase catalytic domain (Cel7B CD) facilitates complexation of cellulose chains from a crystal surface. With direct relevance to the science of biofuel production, this problem also represents a model system of biopolymer processing by proteins in Nature. Interactions of Cel7B CD with a cellulose microfibril along different paths of complexation are characterized by mapping the atomistic fluctuations recorded in free-energy simulations onto the parameters of a coarse-grain model. The resulting patterns of protein-biopolymer couplings also uncover the sequence signatures of the enzyme in peeling off glucan chains from the microfibril substrate. We show that the semiopen active site of Cel7B CD exhibits similar barriers and free energies of complexation over two distinct routes; namely, scooping of a chain into the active-site cleft and threading from the chain end into the channel. On the other hand, the complexation energetics strongly depends on the surface packing of the targeted chain and the resulting interaction sites with the enzyme. A revealed principle is that Cel7B CD facilitates cellulose deconstruction via adaptive coupling to the emergent substrate. The flexible, peripheral segments of the protein outside of the active-site cleft are able to accommodate the varying features of cellulose along the simulated paths of complexation. The general strategy of linking physics-based molecular interactions to protein sequence could also be helpful in elucidating how other protein machines process biopolymers.

  10. Efficient Energy Transfer and Metal Coupling in Cyanide-Bridged Heterodinuclear Complexes Based on (Bipyridine)(terpyridine)ruthenium(II) and (Phenylpyridine)iridium(III) Complexes.

    PubMed

    Barthelmes, Kevin; Jäger, Michael; Kübel, Joachim; Friebe, Christian; Winter, Andreas; Wächtler, Maria; Dietzek, Benjamin; Schubert, Ulrich S

    2016-06-01

    We report a series of cyanide-bridged, heterodinuclear iridium(III)-ruthenium(II) complexes with the generalized formula [Ir((R2)2-ppy)2(CN)(μ-CN)Ru(bpy)(tpy-R1)]PF6 (ppy = 2-phenylpyridine, bpy = 2,2'-bipyridine, and tpy = 2,2':6',2″-terpyridine). The structural, spectroscopic, and electrochemical properties were analyzed in the context of variation of the electron-withdrawing (e.g., -F, -Br, -CHO) and -donating (e.g., -Me) and extended π-conjugated groups at several positions. In total, ten dinuclear complexes and the appropriate model complexes have been prepared. The iridium(III)-based emission is almost fully quenched in these complexes, and only the ruthenium(II)-based emission is observed, which indicates an efficient energy transfer toward the Ru center. Upon oxidation of the Ru center, the fluorinated complexes 2 exhibit a broad intervalence charge-transfer transition in the near-infrared region. The complexes are assigned to a weakly coupled class II system according to the Robin-Day classification. The electronic structure was evaluated by density functional theory (DFT) and time-dependent DFT calculations to corroborate the experimental data. PMID:27214264

  11. Investigating vibrational anharmonic couplings in cyanide-bridged transition metal mixed valence complexes using two-dimensional infrared spectroscopy

    NASA Astrophysics Data System (ADS)

    Slenkamp, Karla M.; Lynch, Michael S.; Van Kuiken, Benjamin E.; Brookes, Jennifer F.; Bannan, Caitlin C.; Daifuku, Stephanie L.; Khalil, Munira

    2014-02-01

    Using polarization-selective two-dimensional infrared (2D IR) spectroscopy, we measure anharmonic couplings and angles between the transition dipole moments of the four cyanide stretching (νCN) vibrations found in [(NH3)5RuIIINCFeII(CN)5]- (FeRu) dissolved in D2O and formamide and [(NC)5FeIICNPtIV(NH3)4NCFeII(CN)5]4- (FePtFe) dissolved in D2O. These cyanide-bridged transition metal complexes serve as model systems for studying the role of high frequency vibrational modes in ultrafast photoinduced charge transfer reactions. Here, we focus on the spectroscopy of the νCN modes in the electronic ground state. The FTIR spectra of the νCN modes of the bimetallic and trimetallic systems are strikingly different in terms of frequencies, amplitudes, and lineshapes. The experimental 2D IR spectra of FeRu and FePtFe and their fits reveal a set of weakly coupled anharmonic νCN modes. The vibrational mode anharmonicities of the individual νCN modes range from 14 to 28 cm-1. The mixed-mode anharmonicities range from 2 to 14 cm-1. In general, the bridging νCN mode is most weakly coupled to the radial νCN mode, which involves the terminal CN ligands. Measurement of the relative transition dipole moments of the four νCN modes reveal that the FeRu molecule is almost linear in solution when dissolved in formamide, but it assumes a bent geometry when dissolved in D2O. The νCN modes are modelled as bilinearly coupled anharmonic oscillators with an average coupling constant of 6 cm-1. This study elucidates the role of the solvent in modulating the molecular geometry and the anharmonic vibrational couplings between the νCN modes in cyanide-bridged transition metal mixed valence complexes.

  12. Fluorescence enhancement of light-harvesting complex 2 from purple bacteria coupled to spherical gold nanoparticles

    SciTech Connect

    Bujak, Ł.; Czechowski, N.; Piatkowski, D.; Litvin, R.; Mackowski, S.; Brotosudarmo, T. H. P.; Pichler, S.; Cogdell, R. J.; Heiss, W.

    2011-10-24

    The influence of plasmon excitations in spherical gold nanoparticles on the optical properties of a light-harvesting complex 2 (LH2) from the purple bacteria Rhodopseudomonas palustris has been studied. Systematic analysis is facilitated by controlling the thickness of a silica layer between Au nanoparticles and LH2 complexes. Fluorescence of LH2 complexes features substantial increase when these complexes are separated by 12 nm from the gold nanoparticles. At shorter distances, non-radiative quenching leads to a decrease of fluorescence emission. The enhancement of fluorescence originates predominantly from an increase of absorption of pigments comprising the LH2 complex.

  13. Fluorescence enhancement of light-harvesting complex 2 from purple bacteria coupled to spherical gold nanoparticles

    NASA Astrophysics Data System (ADS)

    Bujak, Ł.; Czechowski, N.; Piatkowski, D.; Litvin, R.; Mackowski, S.; Brotosudarmo, T. H. P.; Cogdell, R. J.; Pichler, S.; Heiss, W.

    2011-10-01

    The influence of plasmon excitations in spherical gold nanoparticles on the optical properties of a light-harvesting complex 2 (LH2) from the purple bacteria Rhodopseudomonas palustris has been studied. Systematic analysis is facilitated by controlling the thickness of a silica layer between Au nanoparticles and LH2 complexes. Fluorescence of LH2 complexes features substantial increase when these complexes are separated by 12 nm from the gold nanoparticles. At shorter distances, non-radiative quenching leads to a decrease of fluorescence emission. The enhancement of fluorescence originates predominantly from an increase of absorption of pigments comprising the LH2 complex.

  14. Coordination Complexes of Decamethylytterbocene with4,4'-Disubstituted Bipyridines: An Experimental Study of Spin Coupling inLanthanide Complexes

    SciTech Connect

    Walter, Marc D.; Berg, David J.; Andersen, Richard A.

    2005-12-08

    The paramagnetic 1:1 coordination complexes of (C5Me5)2Ybwith a series of 4,4'-disubstituted bipyridines, bipy-X, where X is Me,tert-Bu, OMe, Ph, CO2Me, and CO2Et have been prepared. All of thecomplexes are paramagnetic and the values of the magnetic susceptibilityas a function of temperature show that these values are less thanexpected for the cation, [(C5Me5)2Yb(III)(bipy-X)]+, which have beenisolated as the cation-anion ion-pairs[(C5Me5)2Yb(III)(bipy-X)]+[(C5Me5)2YbI2]f fnfn where X is CO2Et, OMe andMe. The 1H NMR chemical shifts (293 K) for the methine resonances locatedat the 6,6' site in the bipy-X ring show a linear relationship with thevalues of chiT (300 K) for the neutral complexes which illustrates thatthe molecular behavior does not depend upon the phase with one exception,viz., (C5Me5)2Yb(bipy-Me). Single crystals of the 4,4'-dimethylbipyridinecomplex undergo an irreversible, abrupt first order phase change at 228 Kthat shatters the single crystals. The magnetic susceptibility,represented in a delta vs. T plot, on this complex, in polycrystallineform undergoes reversible abrupt changes in the temperature regime 205 -212 K, which is suggested to be due to the way the individual molec ularunits pack in the unit cell. A qualitative model is proposed thataccounts for the sub-normal magnetic moments in theseytterbocene-bipyridine complexes.

  15. Structure of Human G Protein-Coupled Receptor Kinase 2 in Complex with the Kinase Inhibitor Balanol

    SciTech Connect

    Tesmer, John J.G.; Tesmer, Valerie M.; Lodowski, David T.; Steinhagen, Henning; Huber, Jochen

    2010-07-19

    G protein-coupled receptor kinase 2 (GRK2) is a pharmaceutical target for the treatment of cardiovascular diseases such as congestive heart failure, myocardial infarction, and hypertension. To better understand how nanomolar inhibition and selectivity for GRK2 might be achieved, we have determined crystal structures of human GRK2 in complex with G{beta}{gamma} in the presence and absence of the AGC kinase inhibitor balanol. The selectivity of balanol among human GRKs is assessed.

  16. Electrostatic Effects on Proton-Coupled Electron Transfer in Oxomanganese Complexes Inspired by the Oxygen-Evolving Complex of Photosystem II

    PubMed Central

    Amin, Muhamed; Vogt, Leslie; Vassiliev, Serguei; Rivalta, Ivan; Sultan, Mohammad M.; Bruce, Doug; Brudvig, Gary W.; Batista, Victor S.; Gunner, M. R.

    2013-01-01

    The influence of electrostatic interactions on the free energy of proton-coupled-electron-transfer (PCET) in biomimetic oxomanganese complexes inspired by the oxygen-evolving complex (OEC) of photosystem II (PSII), are investigated. The reported study introduces an enhanced Multi-Conformer Continuum Electrostatics (MCCE) model, parameterized at the density functional theory (DFT) level with a classical valence model for the oxomanganese core. The calculated pKas and oxidation midpoint potentials (Ems) match experimental values for eight complexes indicating that purely electrostatic contributions account for most of the observed couplings between deprotonation and oxidation state transitions. We focus on pKas of terminal water ligands in [Mn(II/III)(H2O)6]2+/3+ (1), [Mn(III)(P)(H2O)2]3- (2, P = 5,10,15,20- tetrakis (2,6-dichloro-3-sulfonatophenyl) porphyrinato), [Mn(IV,IV)2(μ-O)2(terpy)2(H2O)2]4+ (3, terpy = 2,2’:6’,2”-terpyridine) and [Mn3(IV,IV,IV)(μ-O)4(phen)4(H2O)2]4+ (4, phen = 1,10-phenanthroline) and the pKas of μ-oxo bridges and Mn Ems in [Mn2(μ-O)2(bpy)4]2+ (5, bpy = 2,2’-bipyridyl), [Mn2(μ-O)2(salpn)2] (6, salpn= N,N′-bis(salicylidene)-1,3-propanediamine), [Mn2(μ-O)2(3,5-di(Cl)-salpn)2] (7) and [Mn2(μ-O)2(3,5-di(NO2)-salpn)2] (8) which are most relevant to PCET mechanisms. The analysis of complexes 6-8 highlights the strong coupling between electron and proton transfers, with any Mn oxidation lowering the pKa of an oxo bridge by 10.5±0.9 pH units. The model also accounts for changes in the Ems due to ligand substituents, such as those in complexes 6-8, due to the electron withdrawing Cl (7) and NO2 (8). The reported study provides the foundation for analysis of electrostatic effects in other oxomanganese complexes and metalloenzymes, where PCET plays a fundamental role in redox-leveling mechanisms. PMID:23570540

  17. Interfacial Charge Transfer in Dye-Sensitized Solar Cells Using SCN-Free Terpyridine-Coordinated Ru Complex Dye and Co Complex Redox Couples.

    PubMed

    Kono, Takahiro; Masaki, Naruhiko; Nishikawa, Masahiro; Tamura, Rei; Matsuzaki, Hiroyuki; Kimura, Mutsumi; Mori, Shogo

    2016-07-01

    The efficiency of dye-sensitized solar cells (DSSCs) using Ru complex dyes and Co complex redox couples has been increased with a strategy to prevent charge recombination via the addition of bulky or lengthy peripheral units to the dyes. However, despite the efforts, most of the DSSCs are still suffering from nonunity quantum efficiency and fast recombination. We examine the effect of SCN ligand, which has been used for many Ru complex dyes and could attract positively charged Co complexes. We find that replacing the ligands with 2,6-bis(2'-(4'-trifluoromethyl)pyrazolyl)pyridine increases the quantum efficiency and electron lifetime. With the combination of the replacement of SCN ligands and the addition of bulky moiety, ∼80% external quantum efficiency is achieved. These suggest that not only the addition of a blocking effect but also the reduction of electrostatic and dispersion forces between dyes and Co complexes are essential to control the charge separation and recombination processes. PMID:27328462

  18. Dynamics of compressional Mach cones in a strongly coupled complex plasma

    SciTech Connect

    Bandyopadhyay, P. Dey, R.; Sen, Abhijit; Kadyan, Sangeeta

    2014-10-15

    Using a Generalised-Hydrodynamic (GH) fluid model, we study the influence of strong coupling induced modification of the fluid compressibility on the dynamics of compressional Mach cones in a dusty plasma medium. A significant structural change of lateral wakes for a given Mach number and Epstein drag force is found in the strongly coupled regime. With the increase of fluid compressibility, the peak amplitude of the normalised perturbed dust density first increases and then decreases monotonically after reaching its maximum value. It is also noticed that the opening angle of the cone structure decreases with the increase of the compressibility of the medium and the arm of the Mach cone breaks up into small structures in the velocity vector profile when the coupling between the dust particles increases.

  19. Morphological communication: exploiting coupled dynamics in a complex mechanical structure to achieve locomotion

    PubMed Central

    Rieffel, John A.; Valero-Cuevas, Francisco J.; Lipson, Hod

    2010-01-01

    Traditional engineering approaches strive to avoid, or actively suppress, nonlinear dynamic coupling among components. Biological systems, in contrast, are often rife with these dynamics. Could there be, in some cases, a benefit to high degrees of dynamical coupling? Here we present a distributed robotic control scheme inspired by the biological phenomenon of tensegrity-based mechanotransduction. This emergence of morphology-as-information-conduit or ‘morphological communication’, enabled by time-sensitive spiking neural networks, presents a new paradigm for the decentralized control of large, coupled, modular systems. These results significantly bolster, both in magnitude and in form, the idea of morphological computation in robotic control. Furthermore, they lend further credence to ideas of embodied anatomical computation in biological systems, on scales ranging from cellular structures up to the tendinous networks of the human hand. PMID:19776146

  20. A highly active water-soluble cross-coupling catalyst based on dendritic polyglycerol N-heterocyclic carbene palladium complexes.

    PubMed

    Meise, Markus; Haag, Rainer

    2008-01-01

    A new water-soluble polyglycerol derivative functionalized with N-heterocyclic carbene palladium complexes was prepared and applied as catalyst for Suzuki cross-coupling reactions in water. The complex displays a metal loading of around 65 metal centers per dendrimeric molecule, which is estimated to contain 130 chelating groups and thus corresponds approximately to the formation of 2:1 NHC/metal complexes. Monomeric analogues were also synthesized to validate the reactivity of the dendritic catalyst. Both types of catalysts were tested with various aryl bromides and arylboronic acids. Turnover frequencies of up to 2586 h(-1) at 80 degrees C were observed with the dendritic catalyst along with turnover numbers of up to 59 000, which are among the highest turnover numbers reported for polymer-supported catalysts in neat water. The dendritic catalyst could be used (reused) in five consecutive reactions without loss in activity. PMID:18702166

  1. Interactions between Redox Complexes and Semiconductor Quantum Dots Coupled via a Peptide Bridge

    PubMed Central

    Medintz, Igor L.; Pons, Thomas; Trammell, Scott A.; Grimes, Amy F.; English, Doug S.; Blanco-Canosa, Juan B.; Dawson, Philip E.; Mattoussi, Hedi

    2009-01-01

    Colloidal quantum dots (QDs) have a large fraction of their atoms arrayed on their surfaces and are capped with bifunctional ligands, which make their photoluminescence highly sensitive to potential charge transfer to, or from, the surrounding environment. In this report, we used peptides as bridges between CdSe-ZnS QDs and metal complexes to promote charge transfer between the metal complexes and QDs. We found that quenching of the QD emission is highly dependent on the relative position of the oxidation levels of QDs and metal complex used; it also traces the number of metal complexes brought in close proximity of the nanocrystal surface. In addition, partial bleaching of the absorption was measured for the QD-metal complex assemblies. These proximity driven interactions were further used to construct sensing assemblies to detect proteolytic enzyme activity. PMID:19049466

  2. The Oedipus Complex as Observed in Work with Couples and Their Children

    ERIC Educational Resources Information Center

    Miller, Lisa

    2004-01-01

    In work with couples where there is a child referred to a Child and Adolescent Mental Health Service, there are opportunities to observe and to work with unresolved Oedipal issues brought by the parents to the task of creating a family. These conflicts can be seen enacted by the child or children, either internally or externally. Examples are…

  3. The Copper-nicotinamide complex: sustainable applications in coupling and cycloaddition reactions

    EPA Science Inventory

    Crystalline copper (II)-nicotinamide complex, synthesized via simple mixing of copper chloride and nicotinamide solution at room temperature, catalyzes the C-S, C-N bond forming and cycloaddition reactions under a variety of sustainable reaction conditions.

  4. FLS-Based Adaptive Synchronization Control of Complex Dynamical Networks With Nonlinear Couplings and State-Dependent Uncertainties.

    PubMed

    Li, Xiao-Jian; Yang, Guang-Hong

    2016-01-01

    This paper is concerned with the problem of synchronization control of complex dynamical networks (CDN) subject to nonlinear couplings and uncertainties. An fuzzy logical system-based adaptive distributed controller is designed to achieve the synchronization. The asymptotic convergence of synchronization errors is analyzed by combining algebraic graph theory and Lyapunov theory. In contrast to the existing results, the proposed synchronization control method is applicable for the CDN with system uncertainties and unknown topology. Especially, the considered uncertainties are allowed to occur in the node local dynamics as well as in the interconnections of different nodes. In addition, it is shown that a unified controller design framework is derived for the CDN with or without coupling delays. Finally, simulations on a Chua's circuit network are provided to validate the effectiveness of the theoretical results. PMID:25720020

  5. Strong Exchange Coupling in a Trimetallic Radical-Bridged Cobalt(II)-Hexaazatrinaphthylene Complex.

    PubMed

    Moilanen, Jani O; Chilton, Nicholas F; Day, Benjamin M; Pugh, Thomas; Layfield, Richard A

    2016-04-25

    Reducing hexaazatrinaphthylene (HAN) with potassium in the presence of 18-c-6 produces [{K(18-c-6)}HAN], which contains the S=1/2 radical [HAN](.-) . The [HAN](.-) radical can be transferred to the cobalt(II) amide [Co{N(SiMe3 )2 }2 ], forming [K(18-c-6)][(HAN){Co(N'')2 }3 ]; magnetic measurements on this compound reveal an S=4 spin system with strong cobalt-ligand antiferromagnetic exchange and J≈-290 cm(-1) (-2 J formalism). In contrast, the Co(II) centres in the unreduced analogue [(HAN){Co(N'')2 }3 ] are weakly coupled (J≈-4.4 cm(-1) ). The finding that [HAN](.-) can be synthesized as a stable salt and transferred to cobalt introduces potential new routes to magnetic materials based on strongly coupled, triangular HAN building blocks. PMID:26997130

  6. Communication: Relativistic Fock-space coupled cluster study of small building blocks of larger uranium complexes

    SciTech Connect

    Tecmer, Paweł Visscher, Lucas; Severo Pereira Gomes, André; Knecht, Stefan

    2014-07-28

    We present a study of the electronic structure of the [UO{sub 2}]{sup +}, [UO{sub 2}]{sup 2} {sup +}, [UO{sub 2}]{sup 3} {sup +}, NUO, [NUO]{sup +}, [NUO]{sup 2} {sup +}, [NUN]{sup −}, NUN, and [NUN]{sup +} molecules with the intermediate Hamiltonian Fock-space coupled cluster method. The accuracy of mean-field approaches based on the eXact-2-Component Hamiltonian to incorporate spin–orbit coupling and Gaunt interactions are compared to results obtained with the Dirac–Coulomb Hamiltonian. Furthermore, we assess the reliability of calculations employing approximate density functionals in describing electronic spectra and quantities useful in rationalizing Uranium (VI) species reactivity (hardness, electronegativity, and electrophilicity)

  7. Red-shifted cyanide stretching frequencies in cyanide-bridged transition metal donor-acceptor complexes. Support for vibronic coupling

    SciTech Connect

    Watzky, M.A.; Endicott, J.F.; Song, X.

    1996-06-05

    Patterns in the cyanide stretching frequencies have been examined in several series of monometal- and CN{sup {minus}} bridged transition metal complexes. Metal-to-cyanide back-bonding can be identified as a major factor contributing to red shifts of v{sub CN} in monometal complexes. This effect is complicated in cyanide-bridged complexes in two ways: (a) when both metals can back-bond to cyanide, the net interaction is repulsive and results in a blue shift of v{sub CN}: and (b) when a donor and acceptor are bridged, V{sub CN} undergoes a substantial red shift (sometimes more than 60 cm{sup {minus}1} lower in energy than the parent monometal complex). These effects can be described by simple perturbational models for the electronic interactions. Monometal cyanide complexes and CN{sup {minus}}-bridged backbonding metals can be treated in terms of their perturbations of the CN{sup {minus}} {pi} and {pi}* orbitals by using a simple, Hueckel-like, three-center perturbational treatment of electronic interactions. However, bridged donor-acceptor pairs are best described by a vibronic model in which it is assumed that the extent of electronic delocalization is in equilibrium with variations of some nuclear coordinates. Consistent with this approach, it is found that (a) the oscillator strength of the donor-acceptor charge transfer (DACT) absorption is roughly proportional to the red shift of v{sub CN} and (b) there are strong symmetry constraints on the coupling.

  8. Investigating vibrational anharmonic couplings in cyanide-bridged transition metal mixed valence complexes using two-dimensional infrared spectroscopy

    SciTech Connect

    Slenkamp, Karla M.; Lynch, Michael S.; Van Kuiken, Benjamin E.; Brookes, Jennifer F.; Bannan, Caitlin C.; Daifuku, Stephanie L.; Khalil, Munira

    2014-02-28

    Using polarization-selective two-dimensional infrared (2D IR) spectroscopy, we measure anharmonic couplings and angles between the transition dipole moments of the four cyanide stretching (ν{sub CN}) vibrations found in [(NH{sub 3}){sub 5}Ru{sup III}NCFe{sup II}(CN){sub 5}]{sup −} (FeRu) dissolved in D{sub 2}O and formamide and [(NC){sub 5}Fe{sup II}CNPt{sup IV}(NH{sub 3}){sub 4}NCFe{sup II}(CN){sub 5}]{sup 4−} (FePtFe) dissolved in D{sub 2}O. These cyanide-bridged transition metal complexes serve as model systems for studying the role of high frequency vibrational modes in ultrafast photoinduced charge transfer reactions. Here, we focus on the spectroscopy of the ν{sub CN} modes in the electronic ground state. The FTIR spectra of the ν{sub CN} modes of the bimetallic and trimetallic systems are strikingly different in terms of frequencies, amplitudes, and lineshapes. The experimental 2D IR spectra of FeRu and FePtFe and their fits reveal a set of weakly coupled anharmonic ν{sub CN} modes. The vibrational mode anharmonicities of the individual ν{sub CN} modes range from 14 to 28 cm{sup −1}. The mixed-mode anharmonicities range from 2 to 14 cm{sup −1}. In general, the bridging ν{sub CN} mode is most weakly coupled to the radial ν{sub CN} mode, which involves the terminal CN ligands. Measurement of the relative transition dipole moments of the four ν{sub CN} modes reveal that the FeRu molecule is almost linear in solution when dissolved in formamide, but it assumes a bent geometry when dissolved in D{sub 2}O. The ν{sub CN} modes are modelled as bilinearly coupled anharmonic oscillators with an average coupling constant of 6 cm{sup −1}. This study elucidates the role of the solvent in modulating the molecular geometry and the anharmonic vibrational couplings between the ν{sub CN} modes in cyanide-bridged transition metal mixed valence complexes.

  9. Dynamical complexity of multipoint geospace observations related to magnetosphere-ionosphere coupling

    NASA Astrophysics Data System (ADS)

    Balasis, Georgios; Daglis, Ioannis A.; Papadimitriou, Constantinos; Donner, Reik; Runge, Jakob

    2016-07-01

    We explore, evaluate and compare the applicability, effectiveness and interdisciplinary character of a variety of modern and sophisticated methods, from complex systems sciences, for the investigation of dynamical complexity of the near-Earth electromagnetic environment. We identify and inter-compare complementary analysis concepts, allowing for a systematic study of geospace magnetic storms and magnetospheric substorms and regime shifts between normal and abnormal states of the Earth's magnetic field, based on observational data from both ground and space. We expect these concepts to allow identifying previously unrecognized precursory structures in the dynamical complexity and, thus, contribute to a better understanding of dynamical processes manifested in observable magnetic field fluctuations prior to possible space weather-related hazards.

  10. Electron-Phonon Coupling and CT-Character in the lowest Triplet Excited State of Anthracene EDA-Complex Crystals

    NASA Astrophysics Data System (ADS)

    Maier, S.; Port, H.

    1987-11-01

    Photoexcitation spectra of triplet (T1← S0) zero-phonon lines and phonon sidebands in different anthracene electron donor-acceptor (EDA) complex crystals (A-PMDA, A-TCNB, A-TCPA) have been analyzed between 1.3 K and 50 K at high spectral resolution. From the electron-phonon coupling strength at T = 0 K values of the charge-transfer (CT) character in the range between 6% and 10% are calculated. The differences in these values are found to be correlated with the energetic positions of the triplet state, which are explained within the framework of the Mulliken theory.

  11. Coordination of 1,4-Diazabutadiene Ligands to Decamethylytterbocene: Additional Examples of Spin Coupling in Ytterbocene Complexes

    SciTech Connect

    Andersen, Richard; Walter, Marc D.; Berg, David J.; Andersen, Richard A.

    2006-11-04

    The paramagnetic 1:1 coordination complexes of (C5Me5)2Yb with a series of diazabutadiene ligands, RN=C(R')C(R')=NR, where R= CMe3, CHMe2, adamantyl, p-tolyl, p-anisyl, and mesityl when R'=H, and R= p-anisyl when R'= Me, have been prepared. The complexes are paramagnetic, but their magnetic moments are less than expected for the two uncoupled spin carriers, (C5Me5)2Yb(III, 4f13) and the diazabutadiene radical anions (S=1/2), which implies exchange coupling between the spins. The variable temperature 1H NMR spectra show that rotation about the R-N bond is hindered and these barriers are estimated. The barriers are largely determined by steric effects but electronic effects are not unimportant.

  12. Double-donor complex in vertically coupled quantum dots in a threading magnetic field.

    PubMed

    Manjarres-García, Ramón; Escorcia-Salas, Gene Elizabeth; Manjarres-Torres, Javier; Mikhailov, Ilia D; Sierra-Ortega, José

    2012-01-01

    We consider a model of hydrogen-like artificial molecule formed by two vertically coupled quantum dots in the shape of axially symmetrical thin layers with on-axis single donor impurity in each of them and with the magnetic field directed along the symmetry axis. We present numerical results for energies of some low-lying levels as functions of the magnetic field applied along the symmetry axis for different quantum dot heights, radii, and separations between them. The evolution of the Aharonov-Bohm oscillations of the energy levels with the increase of the separation between dots is analyzed. PMID:23013550

  13. Photoactivation of Diiodido-Pt(IV) Complexes Coupled to Upconverting Nanoparticles.

    PubMed

    Perfahl, Stefanie; Natile, Marta M; Mohamad, Heba S; Helm, Christiane A; Schulzke, Carola; Natile, Giovanni; Bednarski, Patrick J

    2016-07-01

    The preparation, characterization, and surface modification of upconverting lanthanide-doped hexagonal NaGdF4 nanocrystals attached to light sensitive diiodido-Pt(IV) complexes is presented. The evaluation for photoactivation and cytotoxicity of the novel carboxylated diiodido-Pt(IV) cytotoxic prodrugs by near-infrared (NIR) light (λ = 980 nm) is also reported. We attempted two different strategies for attachment of light-sensitive diiodido-Pt(IV) complexes to Yb,Er- and Yb,Tm-doped β-NaGdF4 upconverting nanoparticles (UCNPs) in order to provide nanohybrids, which offer unique opportunities for selective drug activation within the tumor cells and subsequent spatiotemporal controlled drug release by NIR-to-visible light-upconversion: (A) covalent attachment of the Pt(IV) complex via amide bond formation and (B) carboxylate exchange of oleate on the surface of the UCNPs with diiodido-Pt(IV) carboxylato complexes. Initial feasibility studies showed that NIR applied by a 980 nm laser had only a slight effect on the stability of the various diiodido-Pt(IV) complexes, but when UCNPs were present more rapid loss of the ligand-metal-charge transfer (LMCT) bands of the diiodido-Pt(IV) complexes was observed. Furthermore, Pt released from the Pt(IV) complexes platinated calf-thymus DNA (ct-DNA) more rapidly when NIR was applied compared to dark controls. Of the two attachment strategies, method A with the covalently attached diiodido-Pt(IV) carboxylates via amide bond formation proved to be the most effective method for generating UCNPs that release Pt when irradiated with NIR; the released Pt was also able to bind irreversibly to calf thymus DNA. Nonetheless, only ca. 20% of the Pt on the surface of the UCNPs was in the Pt(IV) oxidation state, the rest was Pt(II), indicating chemical reduction of the diiodido-Pt(IV) prodrug by the UCNPs. Cytotoxicity studies with the various UCNP-Pt conjugates and constructs, tested on human leukemia HL60 cells in culture, indicated a

  14. The coupling of carbon dioxide and epoxides by phenanthroline derivatives containing different Cu(II) complexes as catalyst

    NASA Astrophysics Data System (ADS)

    Kilic, Ahmet; Palali, Ahmet Arif; Durgun, Mustafa; Tasci, Zeynep; Ulusoy, Mahmut

    2013-09-01

    A series of the mononuclear Cu(II) metal complexes containing the ligand Bdppz [(9a,13a-dihydro-4,5,9,14-tetraaza-benzo[b]triphenylene-11-yl)-phenyl-methanone] (L1) and Aqphen [(12,17-dihydronaphthol[2,3-h]dipyrido[3,2-a:2‧,3‧-c]-phenazine-12,17-dione)] (L2) were synthesized and used as catalyst for the coupling of carbon dioxide (CO2) and liquid epoxide which served as both reactant and solvent. Dimethylamino pyridine (DMAP) was used as co-catalyst. The yields of epoxides to corresponding cyclic carbonates were determined by comparing the ratio of product to substrate in the 1H NMR spectrum of an aliquot of the reaction mixture. The mononuclear Cu(II) complexes of these ligands were synthesized by treating an ethanol solvent of the appropriate ligand with a different molar amount of CuCl2·2H2O. The Cu(II) complexes were characterized by FT-IR, UV-Vis, elemental analysis, melting point analysis, mass spectra, molar conductivity measurements and magnetic susceptibility techniques. The reaction of the Bdppz and Aqphen ligands in a 1:1, 1:2 or 1:3 mole ratio with CuCl2·2H2O afforded ionic Cu(II) complexes in the presence of Et3N.

  15. Investigation of organic magnetoresistance dependence on spin-orbit coupling using 8-hydroxyquinolinate rare-earth based complexes

    NASA Astrophysics Data System (ADS)

    Carvalho, R. S.; Costa, D. G.; Ávila, H. C.; Paolini, T. B.; Brito, H. F.; Capaz, Rodrigo B.; Cremona, M.

    2016-05-01

    The recently discovered organic magnetoresistance effect (OMAR) reveals the spin-dependent behavior of the charge transport in organic semiconductors. So far, it is known that hyperfine interactions play an important role in this phenomenon and also that spin-orbit coupling is negligible for light-atom based compounds. However, in the presence of heavy atoms, spin-orbit interactions should play an important role in OMAR. It is known that these interactions are responsible for singlet and triplet states mixing via intersystem crossing and the change of spin-charge relaxation time in the charge mobility process. In this work, we report a dramatic change in the OMAR effect caused by the presence of strong intramolecular spin-orbit coupling in a series of rare-earth quinolate organic complex-based devices. Our data show a different OMAR lineshape compared with the OMAR lineshape of tris(8-hydroxyquinolinate) aluminum-based devices, which are well described in the literature. In addition, electronic structure calculations based on density functional theory help to establish the connection between this results and the presence of heavy central ions in the different complexes.

  16. KCNQ1, KCNE2, and Na+-Coupled Solute Transporters Form Reciprocally Regulating Complexes that Affect Neuronal Excitability

    PubMed Central

    Abbott, Geoffrey W.; Tai, Kwok-Keung; Neverisky, Daniel; Hansler, Alex; Hu, Zhaoyang; Roepke, Torsten K.; Lerner, Daniel J.; Chen, Qiuying; Liu, Li; Zupan, Bojana; Toth, Miklos; Haynes, Robin; Huang, Xiaoping; Demirbas, Didem; Buccafusca, Roberto; Gross, Steven S.; Kanda, Vikram A.; Berry, Gerard T.

    2014-01-01

    Na+-coupled solute transport is crucial for the uptake of nutrients and metabolic precursors, such as myo-inositol, an important osmolyte and precursor for various cell signaling molecules. Here, we found that various solute transporters and potassium channel subunits formed complexes and reciprocally regulated each other in vitro and in vivo. Global metabolite profiling revealed that mice lacking KCNE2, a K+ channel β subunit, showed a reduction in the myo-inositol concentration in cerebrospinal fluid (CSF) but not in serum. Increased behavorial responsiveness to stress and seizure susceptibility in Kcne2−/− mice were alleviated by injections of myo-inositol. Suspecting a defect in myo-inositol transport, we found that KCNE2 and KCNQ1, a voltage-gated potassium channel α subunit, colocalized and coimmunoprecipitated with SMIT1, a Na+-coupled myo-inositol transporter, in the choroid plexus epithelium. Heterologous coexpression demonstrated that myo-inositol transport by SMIT1 was augmented by coexpression of KCNQ1 but inhibited by coexpression of both KCNQ1 and KCNE2, which form a constitutively active, heteromeric K+ channel. SMIT1 and the related transporter SMIT2 were also inhibited by a constitutively active mutant form of KCNQ1. The activity of KCNQ1 and KCNQ1-KCNE2 were augmented by SMIT1 and the glucose transporter SGLT1, but suppressed by SMIT2. Channel-transporter signaling complexes may be a widespread mechanism to facilitate solute transport and electrochemical crosstalk. PMID:24595108

  17. Coupled lagged ensemble weather- and river runoff prediction in complex Alpine terrain

    NASA Astrophysics Data System (ADS)

    Smiatek, Gerhard; Kunstmann, Harald; Werhahn, Johannes

    2013-04-01

    It is still a challenge to predict fast reacting streamflow precipitation response in Alpine terrain. Civil protection measures require flood prediction in 24 - 48 lead time. This holds particularly true for the Ammer River region which was affected by century floods in 1999, 2003 and 2005. Since 2005 a coupled NWP/Hydrology model system is operated in simulating and predicting the Ammer River discharges. The Ammer River catchment is located in the Bavarian Ammergau Alps and alpine forelands, Germany. With elevations reaching 2185 m and annual mean precipitation between 1100 and 2000 mm it represents very demanding test ground for a river runoff prediction system. The one way coupled system utilizes a lagged ensemble prediction system (EPS) taking into account combination of recent and previous NWP forecasts. The major components of the system are the MM5 NWP model run at 3.5 km resolution and initialized twice a day, the hydrology model WaSiM-ETH run at 100 m resolution and Perl object environment (POE) implementing the networking and the system operation. Results obtained in the years 2005-2012 reveal that river runoff simulations depict already high correlation (NSC in range 0.53 and 0.95) with observed runoff in retrospective runs with monitored meteorology data, but suffer from errors in quantitative precipitation forecast (QPF) from the employed numerical weather prediction model. We evaluate the NWP model accuracy, especially the precipitation intensity, frequency and location and put a focus on the performance gain of bias adjustment procedures. We show how this enhanced QFP data help to reduce the uncertainty in the discharge prediction. In addition to the HND (Hochwassernachrichtendienst, Bayern) observations TERENO Longterm Observatory hydrometeorological observation data are available since 2011. They are used to evaluate the NWP performance and setup of a bias correction procedure based on ensemble postprocessing applying Bayesian (BMA) model averaging

  18. Spectroscopic studies of plasmon coupling between photosynthetic complexes and metallic quantum dots

    NASA Astrophysics Data System (ADS)

    Olejnik, Maria; Krajnik, Bartosz; Kowalska, Dorota; Lin, Guanhua; Mackowski, Sebastian

    2013-05-01

    Metallic quantum dots, or nanoparticles, have found an increasing number of applications not only in nanotechnology and nanoscience, but also in neighboring disciplines, such as chemistry and biology. Among the variety of ways to exploit the unique properties of metallic nanostructures is the notion that plasmonic effects associated with the movement of free carriers in metallic nanoparticles may enhance photosynthetic function in naturally evolved organisms. We report on optical microscopy and spectroscopy studies of three hybrid nanostructures composed of spherical gold nanoparticles and peridinin-chlorophyll-protein (PCP), a light-harvesting complex from algae. In the case of a bioconjugated structure we find efficient, concentration dependent quenching due to non-radiative energy transfer. In contrast, for the PCP complexes deposited directly on Au nanoparticles, the emission is increased as a result of the strong increase of the fluorescence quantum yield. Finally, for a structure with controlled separation between metallic nanoparticles and the light-harvesting complexes the emission features non-monotonic behavior with maximum enhancement of about 6, which is due to a combination of fluorescence and absorption rate increases. In this way we demonstrate how the design of plasmonic hybrid nanostructures determines the optical response, which is important for engineering novel systems for photovoltaics and sensor applications, for instance.

  19. Heinrich events modeled with a coupled complex ice sheet-climate model

    NASA Astrophysics Data System (ADS)

    Ziemen, Florian; Rodehacke, Christian; Mikolajewicz Mikolajewicz, Uwe

    2013-04-01

    We investigate glacial climate variability with a coupled ice sheet model (ISM) - atmosphere-ocean-vegetation general circulation model (AOVGCM) system, focusing on one of the most prominent features of glacial climate variability, the Heinrich events. Modeling past climates and periods of past climate change is an important test of the capability of climate models to correctly represent future climate changes. Only if we can correctly represent past climates and climate changes, we can be confident about our predictions of future climate changes. We show results from two experiments: (1) a steady-state LGM experiment where the ice sheet model is accelerated by a factor of 10 compared to the climate model covering 30 kyrs in the ISM (3 kyrs in the AOVGCM) and (2) a synchronously coupled experiment focusing in on one ice sheet collapse covering 3.2 kyrs in both models. For the experiments, we coupled a modified version of the Parallel Ice Sheet Model (mPISM) bidirectionally with the AOVGCM ECHAM5/MPIOM/LPJ. ECHAM5 and LPJ were run in T31 resolution (~ 3.75°), MPIOM on a grid with a nominal resolution of 3° and poles over Greenland and Antarctica, mPISM on a 20 km grid covering most of the northern hemisphere. In the models, as well as in the coupling, no flux correction or anomaly maps are applied. The ice sheet surface mass balance is computed using a positive degree day scheme with lapse rate correction and height desertification effect. In the experiments, the surges of the Hudson Strait Ice Stream reach discharge rates of 60000 m3/s and show a typical recurrence interval of 7 kyrs, matching the basic characteristics for Heinrich events inferred from proxy data. The surges are consequences of an internal instability mechanism suggested by MacAyeal (1993) and various parts of the ice sheets show repeated surging. The large ice discharge during a surge of the Hudson Strait Ice Stream causes an expansion of the sea ice cover in the Labrador Sea and the adjacent

  20. Proton-Coupled Electron Transfer in the Reduction of Carbonyls by Samarium Diiodide-Water Complexes.

    PubMed

    Chciuk, Tesia V; Anderson, William R; Flowers, Robert A

    2016-07-20

    Reduction of carbonyls by SmI2 is significantly impacted by the presence of water, but the fundamental step(s) of initial transfer of a formal hydrogen atom from the SmI2-water reagent system to produce an intermediate radical is not fully understood. In this work, we provide evidence consistent with the reduction of carbonyls by SmI2-water proceeding through proton-coupled electron transfer (PCET). Combined rate and computational studies show that a model aldehyde and ketone are likely reduced through an asynchronous PCET, whereas reduction of a representative lactone occurs through a concerted PCET. In the latter case, concerted PCET is likely a consequence of significantly endergonic initial electron transfer. PMID:27367158

  1. Complex analysis of scattering 1p-shell nuclei in the framework of coupled channel method

    NASA Astrophysics Data System (ADS)

    Nassurlla, M.; Burtebayev, N.; Duisebayev, A.; Burtebayeva, J.; Spitaleri, C.; Urkinbayev, A.; Rusek, K.; Piasecki, E.; Kliczewski, S.; Trzcinska, A.; Sakuta, S. B.; Boztosun, I.; Artemov, S. V.; Galanina, L. I.

    2016-04-01

    The scattering process on 1p-shell nuclei, having the cluster structure, can be seen in the anomaly increasing of cross sections for large angles. Most often, this increasing of cross sections is connected with mechanism of transfer of clusters or nucleons. The study of the α-cluster transfer mechanism in the elastic scattering of 20Ne ions on 16O nuclei is important for investigation burning process in evolution of the Universe immediately after the Big-Bang. Therefore new experiment on the heavy ion accelerator (Warsaw University) was carried out with a significant expansion of the range of angles up to 1700 in center mass system at E Lab =50.0 MeV. Data analysis of angular distribution was performed in framework of the optical model and coupled channel method. The optimal parameters of the optical potential were obtained and the spectroscopic factor was obtained 1 for 20Ne as α +16O.

  2. Sensitivity analysis of complex coupled systems extended to second and higher order derivatives

    NASA Technical Reports Server (NTRS)

    Sobieszczanski-Sobieski, Jaroslaw

    1989-01-01

    In design of engineering systems, the what if questions often arise such as: what will be the change of the aircraft payload, if the wing aspect ratio is incremented by 10 percent. Answers to such questions are commonly sought by incrementing the pertinent variable, and reevaluating the major disciplinary analyses involved. These analyses are contributed by engineering disciplines that are, usually, coupled, as are the aerodynamics, structures, and performance in the context of the question above. The what if questions can be answered precisely by computation of the derivatives. A method for calculation of the first derivatives has been developed previously. An algorithm is presented for calculation of the second and higher order derivatives.

  3. Non-double-couple earthquake mechanisms at the Hengill-Grensdalur volcanic complex, southwest Iceland

    USGS Publications Warehouse

    Julian, B.R.; Miller, A.D.; Foulger, G.R.

    1997-01-01

    The Hengill-Grensdalur area in Iceland generates frequent small non-double-couple earthquakes with explosive volumetric components. We collected high quality three-component digital recordings of 4,000 earthquakes on a purpose-designed, 32-station network in 1991, and determined focal mechanisms for 100 of the best-recorded earthquakes by inverting amplitude ratios. Many of the mechanisms are consistent, within the errors, with simultaneous shear and tensile faulting, with tensile faults parallel to the local spreading ridge, and shear faulting similar to that in the South Iceland transform-fault zone. Some events cannot be explained by this model, however, and require other processes, such as crack closing and partial compensation of tensile cracks by fluid flow.

  4. Exchange coupling transformations in Cu (II) heterospin complexes of “breathing crystals” under structural phase transitions

    SciTech Connect

    Morozov, Vitaly A.; Petrova, Marina V.; Lukzen, Nikita N.

    2015-08-15

    Family of “breathing crystals” is the polymer-chain complexes of Cu(hfac){sub 2} with nitroxides. The polymer chains consist of one-, two- or three-spin clusters. The “breathing crystals” experience simultaneous magnetic and Jahn-Teller type structural phase transitions with change of total cluster spin and drastic change of bond lengths (ca. 10-12%). For the first time the intra-cluster magnetic couplings in ”breathing crystals” have been calculated both by band structure methods GGA + U and hybrid DFT (B3LYP and PBE0) for the isolated exchange clusters. The temperature dependence of the magnetic coupling constant was calculated for two polymer-chain compounds of the “breathing crystal” family - C{sub 21}H{sub 19}CuF{sub 12}N{sub 4}O{sub 6} with the chains containing two-spin clusters and C{sub 22}H{sub 21}CuF{sub 12}N{sub 4}O{sub 6} with the chains of alternating three-spin clusters and one-spin sites. It was found that adding a Hubbard-like parameter not only to the copper 3d electrons but also to the oxygen 2p electrons (GGA + U{sub d} + U{sub p} approach) results in an improved description of exchange coupling in the “breathing crystal” compounds. At the same time treatment of the isolated clusters by a large basis hybrid DFT with high computational cost provides a similar quality fit of the experimental magneto-chemical data as that for the GGA + U{sub d} + U{sub p} band structure calculation scheme. Our calculations also showed that in spite of the abrupt transformation of the magnetic coupling constant under the phase transition, the band gap in the “breathing crystals” remains about the same value with temperature decrease.

  5. Prion Protein—Antibody Complexes Characterized by Chromatography-Coupled Small-Angle X-Ray Scattering

    PubMed Central

    Carter, Lester; Kim, Seung Joong; Schneidman-Duhovny, Dina; Stöhr, Jan; Poncet-Montange, Guillaume; Weiss, Thomas M.; Tsuruta, Hiro; Prusiner, Stanley B.; Sali, Andrej

    2015-01-01

    Aberrant self-assembly, induced by structural misfolding of the prion proteins, leads to a number of neurodegenerative disorders. In particular, misfolding of the mostly α-helical cellular prion protein (PrPC) into a β-sheet-rich disease-causing isoform (PrPSc) is the key molecular event in the formation of PrPSc aggregates. The molecular mechanisms underlying the PrPC-to-PrPSc conversion and subsequent aggregation remain to be elucidated. However, in persistently prion-infected cell-culture models, it was shown that treatment with monoclonal antibodies against defined regions of the prion protein (PrP) led to the clearing of PrPSc in cultured cells. To gain more insight into this process, we characterized PrP-antibody complexes in solution using a fast protein liquid chromatography coupled with small-angle x-ray scattering (FPLC-SAXS) procedure. High-quality SAXS data were collected for full-length recombinant mouse PrP [denoted recPrP(23–230)] and N-terminally truncated recPrP(89–230), as well as their complexes with each of two Fab fragments (HuM-P and HuM-R1), which recognize N- and C-terminal epitopes of PrP, respectively. In-line measurements by fast protein liquid chromatography coupled with SAXS minimized data artifacts caused by a non-monodispersed sample, allowing structural analysis of PrP alone and in complex with Fab antibodies. The resulting structural models suggest two mechanisms for how these Fabs may prevent the conversion of PrPC into PrPSc. PMID:26287631

  6. An affibody in complex with a target protein: Structure and coupled folding

    PubMed Central

    Wahlberg, Elisabet; Lendel, Christofer; Helgstrand, Magnus; Allard, Peter; Dincbas-Renqvist, Vildan; Hedqvist, Anders; Berglund, Helena; Nygren, Per-Åke; Härd, Torleif

    2003-01-01

    Combinatorial protein engineering provides powerful means for functional selection of novel binding proteins. One class of engineered binding proteins, denoted affibodies, is based on the three-helix scaffold of the Z domain derived from staphylococcal protein A. The ZSPA-1 affibody has been selected from a phage-displayed library as a binder to protein A. ZSPA-1 also binds with micromolar affinity to its own ancestor, the Z domain. We have characterized the ZSPA-1 affibody in its uncomplexed state and determined the solution structure of a Z:ZSPA-1 protein–protein complex. Uncomplexed ZSPA-1 behaves as an aggregation-prone molten globule, but folding occurs on binding, and the original (Z) three-helix bundle scaffold is fully formed in the complex. The structural basis for selection and strong binding is a large interaction interface with tight steric and polar/nonpolar complementarity that directly involves 10 of 13 mutated amino acid residues on ZSPA-1. We also note similarities in how the surface of the Z domain responds by induced fit to binding of ZSPA-1 and Ig Fc, respectively, suggesting that the ZSPA-1 affibody is capable of mimicking the morphology of the natural binding partner for the Z domain. PMID:12594333

  7. The NatA Acetyltransferase Couples Sup35 Prion Complexes to the [PSI+] Phenotype

    PubMed Central

    Pezza, John A.; Langseth, Sara X.; Raupp Yamamoto, Rochele; Doris, Stephen M.; Ulin, Samuel P.; Salomon, Arthur R.

    2009-01-01

    Protein-only (prion) epigenetic elements confer unique phenotypes by adopting alternate conformations that specify new traits. Given the conformational flexibility of prion proteins, protein-only inheritance requires efficient self-replication of the underlying conformation. To explore the cellular regulation of conformational self-replication and its phenotypic effects, we analyzed genetic interactions between [PSI+], a prion form of the S. cerevisiae Sup35 protein (Sup35[PSI+]), and the three Nα-acetyltransferases, NatA, NatB, and NatC, which collectively modify ∼50% of yeast proteins. Although prion propagation proceeds normally in the absence of NatB or NatC, the [PSI+] phenotype is reversed in strains lacking NatA. Despite this change in phenotype, [PSI+] NatA mutants continue to propagate heritable Sup35[PSI+]. This uncoupling of protein state and phenotype does not arise through a decrease in the number or activity of prion templates (propagons) or through an increase in soluble Sup35. Rather, NatA null strains are specifically impaired in establishing the translation termination defect that normally accompanies Sup35 incorporation into prion complexes. The NatA effect cannot be explained by the modification of known components of the [PSI+] prion cycle including Sup35; thus, novel acetylated cellular factors must act to establish and maintain the tight link between Sup35[PSI+] complexes and their phenotypic effects. PMID:19073888

  8. Excitonic coupling of chlorophylls in the plant light-harvesting complex LHC-II.

    PubMed Central

    Schubert, Axel; Beenken, Wichard J D; Stiel, Holger; Voigt, Bernd; Leupold, Dieter; Lokstein, Heiko

    2002-01-01

    Manifestation and extent of excitonic interactions in the red Chl-absorption region (Q(y) band) of trimeric LHC-II were investigated using two complementary nonlinear laser-spectroscopic techniques. Nonlinear absorption of 120-fs pulses indicates an increased absorption cross section in the red wing of the Q(y) band as compared to monomeric Chl a in organic solution. Additionally, the dependence of a nonlinear polarization response on the pump-field intensity was investigated. This approach reveals that one emitting spectral form, characterized by a 2.3(+/-0.8)-fold larger dipole strength than monomeric Chl a, dominates the fluorescence spectrum of LHC-II. Considering available structural and spectroscopic data, these results can be consistently explained assuming the existence of an excitonically coupled dimer located at Chl-bindings sites a2 and b2 (referring to the original notation of W. Nühlbrandt, D.N. Wang, and Y. Fujiyoshi, Nature, 1994, 367:614-621), which must not necessarily correspond to Chls a and b). This fluorescent dimer, terminating the excitation energy-transfer chain of the LHC-II monomeric subunit, is discussed with respect to its relevance for intra- and inter-antenna excitation energy transfer. PMID:11806942

  9. An alternative to fully coupled reactive transport simulations for long-term prediction of chemical reactions in complex geological systems

    NASA Astrophysics Data System (ADS)

    De Lucia, Marco; Kempka, Thomas; Kühn, Michael

    2014-05-01

    Fully-coupled reactive transport simulations involving multiphase hydrodynamics and chemical reactions in heterogeneous settings are extremely challenging from a computational point of view. This often leads to oversimplification of the investigated system: coarse spatial discretization, to keep the number of elements in the order of few thousands; simplified chemistry, disregarding many potentially important reactions. A novel approach for coupling non-reactive hydrodynamic simulations with the outcome of single batch geochemical simulations was therefore introduced to assess the potential long-term mineral trapping at the Ketzin pilot site for underground CO2 storage in Germany [1],[2]. The advantage of the coupling is the ability to use multi-million grid non-reactive hydrodynamics simulations on one side and few batch 0D geochemical simulations on the other, so that the complexity of both systems does not need to be reduced. This contribution shows the approach which was taken to validate this simplified coupling scheme. The procedure involved batch simulations of the reference geochemical model, then performing both non-reactive and fully coupled 1D and 3D reactive transport simulations and finally applying the simplified coupling scheme based on the non-reactive and geochemical batch model. The TOUGHREACT/ECO2N [3] simulator was adopted for the validation. The degree of refinement of the spatial grid and the complexity and velocity of the mineral reactions, along with a cut-off value for the minimum concentration of dissolved CO2 allowed to originate precipitates in the simplified approach were found out to be the governing parameters for the convergence of the two schemes. Systematic discrepancies between the approaches are not reducible, simply because there is no feedback between chemistry and hydrodynamics, and can reach 20 % - 30 % in unfavourable cases. However, even such discrepancy is completely acceptable, in our opinion, given the amount of

  10. Complex Coupling of Air Quality and Climate-Relevant Aerosols in a Chemistry-Aerosol Microphysics Model

    NASA Astrophysics Data System (ADS)

    Yoshioka, M.; Carslaw, K. S.; Reddington, C.; Mann, G.

    2013-12-01

    Controlling emissions of aerosols and their precursors to improve air quality will impact the climate through direct and indirect radiative forcing. We have investigated the impacts of changes in a range of aerosol and gas-phase emission fluxes and changes in temperature on air quality and climate change metrics using a global aerosol microphysics and chemistry model, GLOMAP. We investigate how the responses of PM2.5 and cloud condensation nuclei (CCN) are coupled, and how attempts to improve air quality could have inadvertent effects on CCN, clouds and climate. The parameter perturbations considered are a 5°C increase in global temperature, increased or decreased precursor emissions of anthropogenic SO2, NH3, and NOx, and biogenic monoterpenes, and increased or decreased primary emissions of organic and black carbon aerosols from wildfire, fossil fuel, and biofuel. To quantify the interactions, we define a new sensitivity metric in terms of the response of CCN divided by the response of PM in different regions. .Our results show that the coupled chemistry and aerosol processes cause complex responses that will make any co-benefit policy decision problematic. In particular, we show that reducing SO2 emissions effectively reduces surface-level PM2.5 over continental regions in summer when background PM2.5 is high, with a relatively small reduction in marine CCN (and hence indirect radiative cooling over ocean), which is beneficial for near-term climate. Reducing NOx emissions does not improve summertime air quality very effectively but leads to a relatively high reduction of marine CCN. Reducing NH3 emissions has moderate effects on both PM2.5 and CCN. These three species are strongly coupled chemically and microphysically and the effects of changing emissions of one species on mass and size distributions of aerosols are very complex and spatially and temporally variable. For example, reducing SO2 emissions leads to reductions in sulphate and ammonium mass

  11. Intermolecular Photocatalyzed Heck-like Coupling of Unactivated Alkyl Bromides by a Dinuclear Gold Complex.

    PubMed

    Xie, Jin; Li, Jian; Weingand, Vanessa; Rudolph, Matthias; Hashmi, A Stephen K

    2016-08-26

    A practical protocol for a photocatalyzed alkyl-Heck-like reaction of unactivated alkyl bromides and different alkenes promoted by dinuclear gold photoredox catalysis in the presence of an inorganic base is reported. Primary, secondary, and tertiary unactivated alkyl bromides with β-hydrogen can be applied. Esters, aldehydes, ketones, nitriles, alcohols, heterocycles, alkynes, alkenes, ethers, and halogen moieties are all well tolerated. In addition to 1,1-diarylalkenes, silylenolethers and enamides can also be applied, which further increases the synthetic potential of the reaction. The mild reaction conditions, broad substrate scope, and an excellent functional-group tolerance deliver an ideal tool for synthetic chemists that can even be used for challenging late-stage modifications of complex natural products. PMID:27348503

  12. Trajectory Generation and Coupled Numerical Simulation for Thermal Spraying Applications on Complex Geometries

    NASA Astrophysics Data System (ADS)

    Candel, A.; Gadow, R.

    2009-12-01

    For high process reproducibility and optimized coating quality in thermal spray applications on complex geometries, atmospheric plasma spraying and high-velocity oxygen fuel torches are guided by advanced robot systems. The trajectory of the torch, the spray angle, and the relative speed between torch and component are crucial factors which affect the coating microstructure, properties, and, especially, the residual stress distribution. Thus, the requirement of high-performance thermally sprayed coatings with narrow dimensional tolerances leads to challenges in the field of robot-assisted handling, and software tools for efficient trajectory generation and robot programming are demanded. By appropriate data exchange, the automatically generated torch trajectory and speed profile can be integrated in finite element method models to analyze their influence on the heat and mass transfer during deposition. Coating experiments assisted by online diagnostics were performed to validate the developed software tools.

  13. Nonadiabatic dynamics of photoinduced proton-coupled electron transfer in a solvated phenol-amine complex.

    PubMed

    Goyal, Puja; Schwerdtfeger, Christine A; Soudackov, Alexander V; Hammes-Schiffer, Sharon

    2015-02-12

    Photoinduced concerted electron-proton transfer (EPT), denoted photo-EPT, is important for a wide range of energy conversion processes. Transient absorption and Raman spectroscopy experiments on the hydrogen-bonded p-nitrophenylphenol-t-butylamine complex, solvated in 1,2-dichloroethane, suggested that this complex may undergo photo-EPT. The experiments probed two excited electronic states that were interpreted as an intramolecular charge transfer (ICT) state and an EPT state. Herein mixed quantum mechanical/molecular mechanical nonadiabatic surface hopping dynamics is used to investigate the relaxation pathways following photoexcitation. The potential energy surface is generated on the fly with a semiempirical floating occupation molecular orbital complete active space configuration interaction method for the solute molecule and a molecular mechanical force field for the explicit solvent molecules. The free energy curves along the proton transfer coordinate illustrate that proton transfer is thermodynamically and kinetically favorable on the lower-energy excited state but not on the higher-energy excited state, supporting the characterization of these states as EPT and ICT, respectively. The nonadiabatic dynamics simulations indicate that the population decays from the ICT state to the EPT state in ∼100 fs and from the EPT state to the ground state on the slower time scale of ∼1 ps, qualitatively consistent with the experimental measurements. For ∼54% of the trajectories, the proton transfers from the phenol to the amine in ∼400 fs on the EPT state and then transfers back to the phenol rapidly upon decay to the ground state. Thus, these calculations augment the original interpretation of the experimental data by providing evidence of proton transfer on the EPT state prior to decay to the ground state. The fundamental insights obtained from these simulations are also relevant to other photo-EPT processes. PMID:25545667

  14. Dynamics of Complex Systems Built as Coupled Physical, Communication and Decision Layers

    PubMed Central

    Kühnlenz, Florian; Nardelli, Pedro H. J.

    2016-01-01

    This paper proposes a simple model to capture the complexity of multilayer systems where their constituent layers affect, and are affected by, each other. The physical layer is a circuit composed by a power source and resistors in parallel. Every individual agent aims at maximizing its own delivered power by adding, removing or keeping the resistors it has; the delivered power is in turn a non-linear function that depends on the other agents’ behavior, its own internal state, its global state perception, the information received from its neighbors via the communication network and a randomized selfishness. We develop an agent-based simulation to analyze the effects of number of agents (system size), communication network topology, communication errors and the minimum power gain that triggers a behavioral change on the system dynamic. Our results show that a wave-like behavior at macro-level (caused by individual changes in the decision layer) can only emerge for a specific system size. The ratio between cooperators and defectors depends on the minimum gain assumed—lower minimal gains lead to less cooperation, and vice-versa. Different communication network topologies imply different levels of power utilization and fairness at the physical layer, and a certain level of error in the communication layer induces more cooperation. PMID:26730590

  15. Dynamics of Complex Systems Built as Coupled Physical, Communication and Decision Layers.

    PubMed

    Kühnlenz, Florian; Nardelli, Pedro H J

    2016-01-01

    This paper proposes a simple model to capture the complexity of multilayer systems where their constituent layers affect, and are affected by, each other. The physical layer is a circuit composed by a power source and resistors in parallel. Every individual agent aims at maximizing its own delivered power by adding, removing or keeping the resistors it has; the delivered power is in turn a non-linear function that depends on the other agents' behavior, its own internal state, its global state perception, the information received from its neighbors via the communication network and a randomized selfishness. We develop an agent-based simulation to analyze the effects of number of agents (system size), communication network topology, communication errors and the minimum power gain that triggers a behavioral change on the system dynamic. Our results show that a wave-like behavior at macro-level (caused by individual changes in the decision layer) can only emerge for a specific system size. The ratio between cooperators and defectors depends on the minimum gain assumed-lower minimal gains lead to less cooperation, and vice-versa. Different communication network topologies imply different levels of power utilization and fairness at the physical layer, and a certain level of error in the communication layer induces more cooperation. PMID:26730590

  16. Divergent Coupling of Alcohols and Amines Catalyzed by Isoelectronic Hydride Mn(I) and Fe(II) PNP Pincer Complexes.

    PubMed

    Mastalir, Matthias; Glatz, Mathias; Gorgas, Nikolaus; Stöger, Berthold; Pittenauer, Ernst; Allmaier, Günter; Veiros, Luis F; Kirchner, Karl

    2016-08-22

    Herein, we describe an efficient coupling of alcohols and amines catalyzed by well-defined isoelectronic hydride Mn(I) and Fe(II) complexes, which are stabilized by a PNP ligand based on the 2,6-diaminopyridine scaffold. This reaction is an environmentally benign process implementing inexpensive, earth-abundant non-precious metal catalysts, and is based on the acceptorless alcohol dehydrogenation concept. A range of alcohols and amines including both aromatic and aliphatic substrates were efficiently converted in good to excellent isolated yields. Although in the case of Mn selectively imines were obtained, with Fe-exclusively monoalkylated amines were formed. These reactions proceed under base-free conditions and required the addition of molecular sieves. PMID:27377955

  17. Crystal Structure of a Group I Energy Coupling Factor Vitamin Transporter S Component in Complex with Its Cognate Substrate.

    PubMed

    Josts, Inokentijs; Almeida Hernandez, Yasser; Andreeva, Antonina; Tidow, Henning

    2016-07-21

    Energy coupling factor (ECF) transporters are responsible for the uptake of essential scarce nutrients in prokaryotes. This ATP-binding cassette transporter family comprises two subgroups that share a common architecture forming a tripartite membrane protein complex consisting of a translocation component and ATP hydrolyzing module and a substrate-capture (S) component. Here, we present the crystal structure of YkoE from Bacillus subtilis, the S component of the previously uncharacterized group I ECF transporter YkoEDC. Structural and biochemical analyses revealed the constituent residues of the thiamine-binding pocket as well as an unexpected mode of vitamin recognition. In addition, our experimental and bioinformatics data demonstrate major differences between YkoE and group II ECF transporters and indicate how group I vitamin transporter S components have diverged from other group I and group II ECF transporters. PMID:27447050

  18. Multidimensional treatment of stochastic solvent dynamics in photoinduced proton-coupled electron transfer processes: sequential, concerted, and complex branching mechanisms.

    PubMed

    Soudackov, Alexander V; Hazra, Anirban; Hammes-Schiffer, Sharon

    2011-10-14

    A theoretical approach for the multidimensional treatment of photoinduced proton-coupled electron transfer (PCET) processes in solution is presented. This methodology is based on the multistate continuum theory with an arbitrary number of diabatic electronic states representing the relevant charge distributions in a general PCET system. The active electrons and transferring proton(s) are treated quantum mechanically, and the electron-proton vibronic free energy surfaces are represented as functions of multiple scalar solvent coordinates corresponding to the single electron and proton transfer reactions involved in the PCET process. A dynamical formulation of the dielectric continuum theory is used to derive a set of coupled generalized Langevin equations of motion describing the time evolution of these collective solvent coordinates. The parameters in the Langevin equations depend on the solvent properties, such as the dielectric constants, relaxation time, and molecular moment of inertia, as well as the solute properties. The dynamics of selected intramolecular nuclear coordinates, such as the proton donor-acceptor distance or a torsional angle within the PCET complex, may also be included in this formulation. A surface hopping method in conjunction with the Langevin equations of motion is used to simulate the nonadiabatic dynamics on the multidimensional electron-proton vibronic free energy surfaces following photoexcitation. This theoretical treatment enables the description of both sequential and concerted mechanisms, as well as more complex processes involving a combination of these mechanisms. The application of this methodology to a series of model systems corresponding to collinear and orthogonal PCET illustrates fundamental aspects of these different mechanisms and elucidates the significance of proton vibrational relaxation and nonequilibrium solvent dynamics. PMID:22010706

  19. Intermolecular (119)Sn,(31)P Through-Space Spin-Spin Coupling in a Solid Bivalent Tin Phosphido Complex.

    PubMed

    Arras, Janet; Eichele, Klaus; Maryasin, Boris; Schubert, Hartmut; Ochsenfeld, Christian; Wesemann, Lars

    2016-05-01

    A bivalent tin complex [Sn(NP)2] (NP = [(2-Me2NC6H4)P(C6H5)](-)) was prepared and characterized by X-ray diffraction and solution and solid-state nuclear magnetic resonance (NMR) spectroscopy. In agreement with the X-ray structures of two polymorphs of the molecule, (31)P and (119)Sn CP/MAS NMR spectra revealed one crystallographic phosphorus and tin site with through-bond (1)J((117/119)Sn,(31)P) and through-space (TS)J((117/119)Sn,(31)P) spin-spin couplings. Density functional theory (DFT) calculations of the NMR parameters confirm the experimental data. The observation of through-space (TS)J((117/119)Sn,(31)P) couplings was unexpected, as the distances of the phosphorus atoms of one molecule and the tin atom of the neighboring molecule (>4.6 Å) are outside the sum of the van der Waals radii of the atoms P and Sn (4.32 Å). The intermolecular Sn···P separations are clearly too large for bonding interactions, as supported by a natural bond orbital (NBO) analysis. PMID:27071033

  20. Influence of weak vibrational-electronic couplings on 2D electronic spectra and inter-site coherence in weakly coupled photosynthetic complexes

    SciTech Connect

    Monahan, Daniele M.; Whaley-Mayda, Lukas; Fleming, Graham R.; Ishizaki, Akihito

    2015-08-14

    Coherence oscillations measured in two-dimensional (2D) electronic spectra of pigment-protein complexes may have electronic, vibrational, or mixed-character vibronic origins, which depend on the degree of electronic-vibrational mixing. Oscillations from intrapigment vibrations can obscure the inter-site coherence lifetime of interest in elucidating the mechanisms of energy transfer in photosynthetic light-harvesting. Huang-Rhys factors (S) for low-frequency vibrations in Chlorophyll and Bacteriochlorophyll are quite small (S ≤ 0.05), so it is often assumed that these vibrations influence neither 2D spectra nor inter-site coherence dynamics. In this work, we explore the influence of S within this range on the oscillatory signatures in simulated 2D spectra of a pigment heterodimer. To visualize the inter-site coherence dynamics underlying the 2D spectra, we introduce a formalism which we call the “site-probe response.” By comparing the calculated 2D spectra with the site-probe response, we show that an on-resonance vibration with Huang-Rhys factor as small as S = 0.005 and the most strongly coupled off-resonance vibrations (S = 0.05) give rise to long-lived, purely vibrational coherences at 77 K. We moreover calculate the correlation between optical pump interactions and subsequent entanglement between sites, as measured by the concurrence. At 77 K, greater long-lived inter-site coherence and entanglement appear with increasing S. This dependence all but vanishes at physiological temperature, as environmentally induced fluctuations destroy the vibronic mixing.

  1. Reductive Coupling of Diynes at Rhodium Gives Fluorescent Rhodacyclopentadienes or Phosphorescent Rhodium 2,2'-Biphenyl Complexes.

    PubMed

    Sieck, Carolin; Tay, Meng Guan; Thibault, Marie-Hélène; Edkins, Robert M; Costuas, Karine; Halet, Jean-François; Batsanov, Andrei S; Haehnel, Martin; Edkins, Katharina; Lorbach, Andreas; Steffen, Andreas; Marder, Todd B

    2016-07-18

    Reactions of [Rh(κ(2) -O,O-acac)(PMe3 )2 ] (acac=acetylacetonato) and α,ω-bis(arylbutadiynyl)alkanes afford two isomeric types of MC4 metallacycles with very different photophysical properties. As a result of a [2+2] reductive coupling at Rh, 2,5-bis(arylethynyl)rhodacyclopentadienes (A) are formed, which display intense fluorescence (Φ=0.07-0.54, τ=0.2-2.5 ns) despite the presence of the heavy metal atom. Rhodium biphenyl complexes (B), which show exceptionally long-lived (hundreds of μs) phosphorescence (Φ=0.01-0.33) at room temperature in solution, have been isolated as a second isomer originating from an unusual [4+2] cycloaddition reaction and a subsequent β-H-shift. We attribute the different photophysical properties of isomers A and B to a higher excited state density and a less stabilized T1 state in the biphenyl complexes B, allowing for more efficient intersystem crossing S1 →Tn and T1 →S0 . Control of the isomer distribution is achieved by modification of the bis- (diyne) linker length, providing a fundamentally new route to access photoactive metal biphenyl compounds. PMID:27355689

  2. Serum Response Factor-GATA Ternary Complex Required for Nuclear Signaling by a G-Protein-Coupled Receptor

    PubMed Central

    Morin, Steves; Paradis, Pierre; Aries, Anne; Nemer, Mona

    2001-01-01

    Endothelins are a family of biologically active peptides that are critical for development and function of neural crest-derived and cardiovascular cells. These effects are mediated by two G-protein-coupled receptors and involve transcriptional regulation of growth-responsive and/or tissue-specific genes. We have used the cardiac ANF promoter, which represents the best-studied tissue-specific endothelin target, to elucidate the nuclear pathways responsible for the transcriptional effects of endothelins. We found that cardiac-specific response to endothelin 1 (ET-1) requires the combined action of the serum response factor (SRF) and the tissue-restricted GATA proteins which bind over their adjacent sites, within a 30-bp ET-1 response element. We show that SRF and GATA proteins form a novel ternary complex reminiscent of the well-characterized SRF-ternary complex factor interaction required for transcriptional induction of c-fos in response to growth factors. In transient cotransfections, GATA factors and SRF synergistically activate atrial natriuretic factor and other ET-1-inducible promoters that contain both GATA and SRF binding sites. Thus, GATA factors may represent a new class of tissue-specific SRF accessory factors that account for muscle- and other cell-specific SRF actions. PMID:11158291

  3. Explicitly correlated coupled cluster calculations for the benzenium ion (C6H7(+)) and its complexes with Ne and Ar.

    PubMed

    Botschwina, Peter; Oswald, Rainer

    2011-11-24

    Explicitly correlated coupled cluster theory at the CCSD(T)-F12x (x = a, b) level (Adler, T. B.; Knizia, G.; Werner, H.-J. J. Chem. Phys. 2007, 127, 221106) has been employed in a study of the benzenium ion (C6H7(+)) and its complexes with a neon or an argon atom. The ground-state rotational constants of C6H7(+) are predicted to be A0 = 5445 MHz, B0 = 5313 MHz, and C0 = 2731 MHz. Anharmonic vibrational wavenumbers of this cation were obtained by combination of harmonic CCSD(T*)-F12a values with anharmonic contributions calculated by double-hybrid density functional theory at the B2PLYP-D level. For the complexes of C6H7(+) with Ne or Ar, the lowest energy minimum is of π-bonded structure. The corresponding dissociation energies D0 are estimated to be 160 and 550 cm(-1), respectively. There is no indication of H-bonds to the aromatic or aliphatic hydrogen atoms. Instead, three nonequivalent local energy minima were found for nuclear configurations where the rare-gas atom lies in the ring-plane and approximatly points to the center of one of the six CC bonds. PMID:21981720

  4. Solution NMR Experiment for Measurement of (15)N-(1)H Residual Dipolar Couplings in Large Proteins and Supramolecular Complexes.

    PubMed

    Eletsky, Alexander; Pulavarti, Surya V S R K; Beaumont, Victor; Gollnick, Paul; Szyperski, Thomas

    2015-09-01

    NMR residual dipolar couplings (RDCs) are exquisite probes of protein structure and dynamics. A new solution NMR experiment named 2D SE2 J-TROSY is presented to measure N-H RDCs for proteins and supramolecular complexes in excess of 200 kDa. This enables validation and refinement of their X-ray crystal and solution NMR structures and the characterization of structural and dynamic changes occurring upon complex formation. Accurate N-H RDCs were measured at 750 MHz (1)H resonance frequency for 11-mer 93 kDa (2)H,(15)N-labeled Trp RNA-binding attenuator protein tumbling with a correlation time τc of 120 ns. This is about twice as long as that for the most slowly tumbling system, for which N-H RDCs could be measured, so far, and corresponds to molecular weights of ∼200 kDa at 25 °C. Furthermore, due to the robustness of SE2 J-TROSY with respect to residual (1)H density from exchangeable protons, increased sensitivity at (1)H resonance frequencies around 1 GHz promises to enable N-H RDC measurement for even larger systems. PMID:26293598

  5. Determination of local optical response functions of nanostructures with increasing complexity by using single and coupled Lorentzian oscillator models

    NASA Astrophysics Data System (ADS)

    Aeschlimann, Martin; Brixner, Tobias; Fischer, Alexander; Hensen, Matthias; Huber, Bernhard; Kilbane, Deirdre; Kramer, Christian; Pfeiffer, Walter; Piecuch, Martin; Thielen, Philip

    2016-07-01

    We reconstruct the optical response of nanostructures of increasing complexity by fitting interferometric time-resolved photoemission electron microscopy (PEEM) data from an ultrashort (21 fs) laser excitation source with different harmonic oscillator-based models. Due to its high spatial resolution of ~40 nm, PEEM is a true near-field imaging system and enables in normal incidence mode a mapping of plasmon polaritons and an intuitive interpretation of the plasmonic behaviour. Using an actively stabilized Mach-Zehnder interferometer, we record two-pulse correlation signals with 50 as time resolution that contain information about the temporal plasmon polariton evolution. Spectral amplitude and phase of excited plasmon polaritons are extracted from the recorded phase-resolved interferometric two-pulse correlation traces. We show that the optical response of a plasmon polariton generated at a gold nanoparticle can be reconstructed from the interferometric two-pulse correlation signal using a single harmonic oscillator model. In contrast, for a corrugated silver surface, a system with increased plasmonic complexity, in general an unambiguous reconstruction of the local optical response based on coupled and uncoupled harmonic oscillators, fails. Whereas for certain local responses different models can be discriminated, this is impossible for other positions. Multidimensional spectroscopy offers a possibility to overcome this limitation.

  6. Electron Transfer Reactivity of the Aqueous Iron(IV)-Oxo Complex. Outer-Sphere vs Proton-Coupled Electron Transfer.

    PubMed

    Bataineh, Hajem; Pestovsky, Oleg; Bakac, Andreja

    2016-07-01

    The kinetics of oxidation of organic and inorganic reductants by aqueous iron(IV) ions, Fe(IV)(H2O)5O(2+) (hereafter Fe(IV)aqO(2+)), are reported. The substrates examined include several water-soluble ferrocenes, hexachloroiridate(III), polypyridyl complexes M(NN)3(2+) (M = Os, Fe and Ru; NN = phenanthroline, bipyridine and derivatives), HABTS(-)/ABTS(2-), phenothiazines, Co(II)(dmgBF2)2, macrocyclic nickel(II) complexes, and aqueous cerium(III). Most of the reductants were oxidized cleanly to the corresponding one-electron oxidation products, with the exception of phenothiazines which produced the corresponding oxides in a single-step reaction, and polypyridyl complexes of Fe(II) and Ru(II) that generated ligand-modified products. Fe(IV)aqO(2+) oxidizes even Ce(III) (E(0) in 1 M HClO4 = 1.7 V) with a rate constant greater than 10(4) M(-1) s(-1). In 0.10 M aqueous HClO4 at 25 °C, the reactions of Os(phen)3(2+) (k = 2.5 × 10(5) M(-1) s(-1)), IrCl6(3-) (1.6 × 10(6)), ABTS(2-) (4.7 × 10(7)), and Fe(cp)(C5H4CH2OH) (6.4 × 10(7)) appear to take place by outer sphere electron transfer (OSET). The rate constants for the oxidation of Os(phen)3(2+) and of ferrocenes remained unchanged in the acidity range 0.05 < [H(+)] < 0.10 M, ruling out prior protonation of Fe(IV)aqO(2+) and further supporting the OSET assignment. A fit to Marcus cross-relation yielded a composite parameter (log k22 + E(0)Fe/0.059) = 17.2 ± 0.8, where k22 and E(0)Fe are the self-exchange rate constant and reduction potential, respectively, for the Fe(IV)aqO(2+)/Fe(III)aqO(+) couple. Comparison with literature work suggests k22 < 10(-5) M(-1) s(-1) and thus E(0)(Fe(IV)aqO(2+)/Fe(III)aqO(+)) > 1.3 V. For proton-coupled electron transfer, the reduction potential is estimated at E(0) (Fe(IV)aqO(2+), H(+)/Fe(III)aqOH(2+)) ≥ 1.95 V. PMID:27320290

  7. A coupled remote sensing and the Surface Energy Balance with Topography Algorithm (SEBTA) to estimate actual evapotranspiration under complex terrain

    NASA Astrophysics Data System (ADS)

    Gao, Z. Q.; Liu, C. S.; Gao, W.; Chang, N. B.

    2010-07-01

    Evapotranspiration (ET) may be used as an ecological indicator to address the ecosystem complexity. The accurate measurement of ET is of great significance for studying environmental sustainability, global climate changes, and biodiversity. Remote sensing technologies are capable of monitoring both energy and water fluxes on the surface of the Earth. With this advancement, existing models, such as SEBAL, S_SEBI and SEBS, enable us to estimate the regional ET with limited temporal and spatial scales. This paper extends the existing modeling efforts with the inclusion of new components for ET estimation at varying temporal and spatial scales under complex terrain. Following a coupled remote sensing and surface energy balance approach, this study emphasizes the structure and function of the Surface Energy Balance with Topography Algorithm (SEBTA). With the aid of the elevation and landscape information, such as slope and aspect parameters derived from the digital elevation model (DEM), and the vegetation cover derived from satellite images, the SEBTA can fully account for the dynamic impacts of complex terrain and changing land cover in concert with some varying kinetic parameters (i.e., roughness and zero-plane displacement) over time. Besides, the dry and wet pixels can be recognized automatically and dynamically in image processing thereby making the SEBTA more sensitive to derive the sensible heat flux for ET estimation. To prove the application potential, the SEBTA was carried out to present the robust estimates of 24 h solar radiation over time, which leads to the smooth simulation of the ET over seasons in northern China where the regional climate and vegetation cover in different seasons compound the ET calculations. The SEBTA was validated by the measured data at the ground level. During validation, it shows that the consistency index reached 0.92 and the correlation coefficient was 0.87.

  8. Improving the WRF model's simulation over sea ice surface through coupling with a complex thermodynamic sea ice model

    NASA Astrophysics Data System (ADS)

    Yao, Y.; Huang, J.; Luo, Y.; Zhao, Z.

    2015-12-01

    Sea ice plays an important role in the air-ice-ocean interaction, but it is often represented simply in many regional atmospheric models. The Noah sea ice model, which has been widely used in the Weather Research and Forecasting (WRF) model, exhibits cold bias in simulating the Arctic sea ice temperature when validated against the Surface Heat Budget of the Arctic Ocean (SHEBA) in situ observations. According to sensitivity tests, this bias is attributed not only to the simulation of snow depth and turbulent fluxes but also to the heat conduction within snow and ice. Compared with the Noah sea ice model, the high-resolution thermodynamic snow and ice model (HIGHTSI) has smaller bias in simulating the sea ice temperature. HIGHTSI is further coupled with the WRF model to evaluate the possible added value from better resolving the heat transport and solar penetration in sea ice from a complex thermodynamic sea ice model. The cold bias in simulating the surface temperature over sea ice in winter by the original Polar WRF is reduced when HIGHTSI rather than Noah is coupled with the WRF model, and this also leads to a better representation of surface upward longwave radiation and 2 m air temperature. A discussion on the impact of specifying sea ice thickness in the WRF model is presented. Consistent with previous research, prescribing the sea ice thickness with observational information would result in the best simulation among the available methods. If no observational information is available, using an empirical method based on the relationship between sea ice concentration and sea ice thickness could mimic the large-scale spatial feature of sea ice thickness. The potential application of a thermodynamic sea ice model in predicting the change in sea ice thickness in a RCM is limited by the lack of sea ice dynamic processes in the model and the coarse assumption on the initial value of sea ice thickness.

  9. Functional Importance of a Structurally Distinct Homodimeric Complex of the Family B G Protein-Coupled Secretin Receptor

    PubMed Central

    Gao, Fan; Harikumar, Kaleeckal G.; Dong, Maoqing; Lam, Polo C.-H.; Sexton, Patrick M.; Christopoulos, Arthur; Bordner, Andrew; Abagyan, Ruben; Miller, Laurence J.

    2009-01-01

    Oligomerization of G protein-coupled receptors has been described, but its structural basis and functional importance have been inconsistent. Here, we demonstrate that the agonist occupied wild-type secretin receptor is predominantly in a guanine nucleotide-sensitive high-affinity state and exhibits negative cooperativity, whereas the monomeric receptor is primarily in a guanine nucleotide-insensitive lower affinity state. We previously demonstrated constitutive homodimerization of this receptor through the lipid-exposed face of transmembrane (TM) IV. We now use cysteine-scanning mutagenesis of 14 TM IV residues, bioluminescence resonance energy transfer (BRET), and functional analysis to map spatial approximations and functional importance of specific residues in this complex. All, except for three helix-facing mutants, trafficked to the cell surface, where secretin was shown to bind and elicit cAMP production. Cells expressing complementary-tagged receptors were treated with cuprous phenanthroline to establish disulfide bonds between spatially approximated cysteines. BRET was measured as an indication of receptor oligomerization and was repeated after competitive disruption of oligomers with TM IV peptide to distinguish covalent from noncovalent associations. Although all constructs generated a significant BRET signal, this was disrupted by peptide in all except for single-site mutants replacing five residues with cysteine. Of these, covalent stabilization of receptor homodimers through positions of Gly243, Ile247, and Ala250 resulted in a GTP-sensitive high-affinity state of the receptor, whereas the same procedure with Ala246 and Phe240 mutants resulted in a GTP-insensitive lower affinity state. We propose the existence of a functionally important, structurally specific high-affinity dimeric state of the secretin receptor, which may be typical of family B G protein-coupled receptors. PMID:19429716

  10. Efficient cross-coupling of aryl Grignard reagents with alkyl halides by recyclable ionic iron(III) complexes bearing a bis(phenol)-functionalized benzimidazolium cation.

    PubMed

    Xia, Chong-Liang; Xie, Cun-Fei; Wu, Yu-Feng; Sun, Hong-Mei; Shen, Qi; Zhang, Yong

    2013-12-14

    A novel bis(phenol)-functionalized benzimidazolium salt, 1,3-bis(3,5-di-tert-butyl-2-hydroxybenzyl)benzimidazolium chloride (H3LCl, 1), was designed and used to prepare ionic iron(III) complexes of the type [H3L][FeX4] (X = Cl, 2; X = Br, 3). Both 2 and 3 were characterized by elemental analysis, Raman spectroscopy, electrospray ionization mass spectrometry and X-ray crystallography. The catalytic performances of 2 and 3 in cross-coupling reactions using aryl Grignard reagents with primary and secondary alkyl halides bearing β-hydrogens were studied. This analysis shows that complex 2 has good potential for alkyl chloride-mediated coupling. In comparison, complex 3 showed slightly lower catalytic activity. After decanting the product contained in the ethereal layer, complex 2 could be recycled at least eight times without significant loss of catalytic activity. PMID:24145602

  11. Pretreatment procedures for characterization of arsenic and selenium species in complex samples utilizing coupled techniques with mass spectrometric detection.

    PubMed

    Wrobel, Katarzyna; Wrobel, Kazimierz; Caruso, Joseph A

    2005-01-01

    Research interest in analyzing arsenic and selenium is dictated by their species-dependent behavior in the environment and in living organisms. Different analytical methodologies for known species in relatively simple chemical systems are well established, yet the analysis of complex samples is still a challenge. Owing to the complex matrix and low concentrations of target species that may be chemically labile, suitable pretreatment of the sample becomes a critical step in any speciation procedure. In this paper, the pretreatment procedures used for arsenic and selenium speciation are reviewed with the emphasis on the link between the analytical protocol applied and the biologically-significant information provided by the results obtained. In the first approach, the aim of pretreatment is to convert the original sample into a form that can be analyzed by a coupled (hyphenated) technique, preventing possible losses and/or species interconversion. Common techniques include different leaching and extraction modes, enzymatic hydrolysis, species volatilization, and so on, with or without species preconcentration. On the other hand, if the speciation analysis is performed for elucidation of elemental pathways and specific functions in a living system, more conscious pretreatment and/or fractionation is needed. The macroscopic separation of organs and tissues, isolation of certain types of cells, cell disruption and separation of sub-cellular fractions, as well as isolation of a specific biomolecules become important. Furthermore, to understand molecular mechanisms, the identification of intermediate-often highly instable--metabolites is necessary. Real life applications are reviewed in this work for aquatic samples, soils and sediments, plants, yeast, and urine. PMID:15662512

  12. Phospholamban Modulates the Functional Coupling between Nucleotide Domains in Ca-ATPase Oligomeric Complexes in Cardiac Sarcoplasmic Reticulum

    SciTech Connect

    Chen, L.; Yao, Qing; Soares, Thereza A.; Squier, Thomas C.; Bigelow, Diana J.

    2009-03-24

    Oligomeric interactions between Ca-ATPase polypeptide chains and their modulation by phospholamban (PLB) were measured in native cardiac sarcoplasmic reticulum (SR) microsomes. Progressive modification of Lys514 with fluorescein-5-isothiocyanate (FITC), which physically blocks access to the nucleotide binding site by ATP, demonstrates that Ca-ATPase active sites function independently of one another prior to the phosphorylation of PLB. However, upon PKA-dependent phosphorylation of PLB, a second-order dependence between enzyme activity and the fraction of active sites is observed, consistent with a dimeric functional complex. Complementary distance measurements were made using FITC or 5-iodoacetamido-fluorescein (IAF) bound to Cys674 within the N- or P-domains respectively, to detect structural coupling within oligomeric complexes. Accompanying the phosphorylation of PLB, neighboring Ca-ATPase polypeptide chains exhibit a 4 ± 2 Å decrease in the proximity between FITC sites within the N-domain and a 9 ± 3 Å increase in the proximity between IAF sites within P-domains. Thus, the phosphorylation of PLB induces spatial rearrangements between the N- and P-domain elements of proximal Ca-ATPase polypeptide chains which restore functional interactions between neighboring polypeptide chains and, in turn, result in increased rates of catalytic turnover. These results are interpreted in terms of a structural model, calculated through optimization of shape complementarity, desolvation, and electrostatic energies, which suggests a dimeric arrangement of Ca-ATPase polypeptide chains through the proximal association of N-domains. We suggest that the phosphorylation of PLB acts to release constraints involving interdomain subunit interactions that enhance catalytically important N-domain motions.

  13. Critical coupling and coherent perfect absorption for ranges of energies due to a complex gain and loss symmetric system

    SciTech Connect

    Hasan, Mohammad; Ghatak, Ananya; Mandal, Bhabani Prasad

    2014-05-15

    We consider a non-Hermitian medium with a gain and loss symmetric, exponentially damped potential distribution to demonstrate different scattering features analytically. The condition for critical coupling (CC) for unidirectional wave and coherent perfect absorption (CPA) for bidirectional waves are obtained analytically for this system. The energy points at which total absorption occurs are shown to be the spectral singular points for the time reversed system. The possible energies at which CC occurs for left and right incidence are different. We further obtain periodic intervals with increasing periodicity of energy for CC and CPA to occur in this system. -- Highlights: •Energy ranges for CC and CPA are obtained explicitly for complex WS potential. •Analytical conditions for CC and CPA for PT symmetric WS potential are obtained. •Conditions for left and right CC are shown to be different. •Conditions for CC and CPA are shown to be that of SS for the time reversed system. •Our model shows the great flexibility of frequencies for CC and CPA.

  14. Quasilongitudinal soliton in a two-dimensional strongly coupled complex dusty plasma in the presence of an external magnetic field.

    PubMed

    Ghosh, Samiran

    2014-09-01

    The propagation of a nonlinear low-frequency mode in two-dimensional (2D) monolayer hexagonal dusty plasma crystal in presence of external magnetic field and dust-neutral collision is investigated. The standard perturbative approach leads to a 2D Korteweg-de Vries (KdV) soliton for the well-known dust-lattice mode. However, the Coriolis force due to crystal rotation and Lorentz force due to magnetic field on dust particles introduce a linear forcing term, whereas dust-neutral drag introduce the usual damping term in the 2D KdV equation. This new nonlinear equation is solved both analytically and numerically to show the competition between the linear forcing and damping in the formation of quasilongitudinal soliton in a 2D strongly coupled complex (dusty) plasma. Numerical simulation on the basis of the typical experimental plasma parameters and the analytical solution reveal that the neutral drag force is responsible for the usual exponential decay of the soliton, whereas Coriolis and/or Lorentz force is responsible for the algebraic decay as well as the oscillating tail formation of the soliton. The results are discussed in the context of the plasma crystal experiment. PMID:25314548

  15. Electrochemical proton-coupled electron transfer of an osmium aquo complex: theoretical analysis of asymmetric tafel plots and transfer coefficients.

    PubMed

    Ludlow, Michelle K; Soudackov, Alexander V; Hammes-Schiffer, Sharon

    2010-02-01

    Electrochemical proton-coupled electron transfer of an osmium aquo complex attached to a self-assembled monolayer on a gold electrode is studied with a recently developed theoretical formulation. The calculated hydrogen/deuterium kinetic isotope effect for the standard rate constant, the cathodic transfer coefficient at zero overpotential, and the Tafel plot are in excellent agreement with experimental data. The input quantities to the heterogeneous rate constant expressions were calculated with density functional theory in conjunction with dielectric continuum models, and no parameters were fit to experimental data. The theoretical calculations indicate that the asymmetry of the Tafel plot and the deviation of the transfer coefficient at zero overpotential from the standard value of one-half arise from the change in the equilibrium proton donor-acceptor distance upon electron transfer. The direction of the asymmetry and deviation from one-half is determined by the sign of this distance change, and the magnitude of these effects is determined by the magnitude of this distance change, as well as the reorganization energy and the distance dependence of the overlap between the initial and final proton vibrational wave functions. This theory provides experimentally testable predictions for the impact of specific system properties on the qualitative behavior of the Tafel plots. PMID:20067257

  16. Rapid Isolation and Determination of Flavones in Biological Samples Using Zinc Complexation Coupled with High-Performance Liquid Chromatography.

    PubMed

    Sun, Chenghe; Wang, Hecheng; Wang, Yingping; Xiao, Shengyuan

    2016-01-01

    Chlorophyll-type contaminants are commonly encountered in the isolation and determination of flavones of plant aerial plant parts. Heme is also a difficult background substance in whole blood analysis. Both chlorophyll and heme are porphyrin type compounds. In this study, a rapid method for isolating flavones with 5-hydroxyl or ortho-hydroxyl groups from biological samples was developed based on the different solubilities of porphyrin-metal and flavone-metal complexes. It is important that other background substances, e.g., proteins and lipids, are also removed from flavones without an additional processing. The recoveries of scutellarin, baicalin, baicalein, wogonoside and wogonin, which are the primary constituents of Scutellaria baicalensis (skullcaps) were 99.65% ± 1.02%, 98.98% ± 0.73%, 99.65% ± 0.03%, 97.59% ± 0.09% and 95.19% ± 0.47%, respectively. As a sample pretreatment procedure, this method was coupled to high-performance liquid chromatography (HPLC) with good separation, sensitivity and linearity and was applied to determine the flavone content in different aerial parts of S. baicalensis and in dried blood spot samples. PMID:27537870

  17. Assessing coupling between lakes and layered aquifers in a complex Pleistocene landscape based on water level dynamics

    NASA Astrophysics Data System (ADS)

    Lischeid, Gunnar; Natkhin, Marco; Steidl, Jörg; Dietrich, Ottfried; Dannowski, Ralf; Merz, Christoph

    2010-11-01

    The biosphere reserve Schorfheide-Chorin is a scenic region with many lakes. Hydraulic coupling between lakes and groundwater is difficult to assess due to the very heterogeneous Pleistocene deposits with a complex layering of different aquifers, part of them being confined. Thus, a principal component analysis of time series of groundwater and lake water levels was performed. The first two principal components provided a quantitative measure of damping of the input signal, i.e., the extent to which time series of groundwater pressure heads or lake water levels are smoothed and delayed with respect to the input signal, i.e., groundwater recharge or precipitation minus evapotranspiration, respectively. The lakes differed substantially with respect to damping behaviour, indicating different impacts of deep groundwater contribution. For most of the groundwater wells, damping increased linearly with mean depth to water table. In contrast, some wells exhibited nearly identical behaviour independent of depth. High-pass filtered data of water table level from these wells were strongly and inversely correlated with those of barometric pressure fluctuations, pointing to a confined aquifer which was evidently not connected to the adjacent lake.

  18. Fast, Accurate Simulation of Polaron Dynamics and Multidimensional Spectroscopy by Multiple Davydov Trial States.

    PubMed

    Zhou, Nengji; Chen, Lipeng; Huang, Zhongkai; Sun, Kewei; Tanimura, Yoshitaka; Zhao, Yang

    2016-03-10

    By employing the Dirac-Frenkel time-dependent variational principle, we study the dynamical properties of the Holstein molecular crystal model with diagonal and off-diagonal exciton-phonon coupling. A linear combination of the Davydov D1 (D2) ansatz, referred to as the "multi-D1 ansatz" ("multi-D2 ansatz"), is used as the trial state with enhanced accuracy but without sacrificing efficiency. The time evolution of the exciton probability is found to be in perfect agreement with that of the hierarchy equations of motion, demonstrating the promise the multiple Davydov trial states hold as an efficient, robust description of dynamics of complex quantum systems. In addition to the linear absorption spectra computed for both diagonal and off-diagonal cases, for the first time, 2D spectra have been calculated for systems with off-diagonal exciton-phonon coupling by employing the multiple D2 ansatz to compute the nonlinear response function, testifying to the great potential of the multiple D2 ansatz for fast, accurate implementation of multidimensional spectroscopy. It is found that the signal exhibits a single peak for weak off-diagonal coupling, while a vibronic multipeak structure appears for strong off-diagonal coupling. PMID:26871592

  19. Amidino ligands obtained from the coupling of 1-methylcytosine and nitrile: a new method to incorporate biomolecules into luminescent Re(CO)3 complexes.

    PubMed

    Gómez-Iglesias, Patricia; Martín-Alvarez, Jose Miguel; Miguel, Daniel; Villafañe, Fernando

    2015-10-28

    The formation of an amidino chelating ligand from the coupling reaction of 1-methylcytosine and nitrile is a new method herein reported for the incorporation of biologically relevant substrates into rhenium(i) tricarbonyl complexes. The reactions are carried out thermally or are microwave assisted. PMID:26403763

  20. A Well-Defined {[(PhCH₂O)₂P(CH₃)₂CHNCH(CH₃)₂]₂PdCl₂} Complex Catalyzed Hiyama Coupling of Aryl Bromides with Arylsilanes.

    PubMed

    Guo, Mengping; Fu, Leiqing; Li, Jiamin; Zhou, Lanjiang; Kang, Yanping

    2016-01-01

    A palladium (II) complex {[(PhCH₂O)₂P(CH₃)₂CHNCH(CH₃)₂]₂PdCl₂} catalyzed Hiyama cross-coupling reaction between aryl bromides and arylsilanes has been developed. The substituted biaryls were produced in moderate to high yields, regardless of electron-withdrawing or electron-donating. PMID:27483226

  1. Complex image method for RF antenna-plasma inductive coupling calculation in planar geometry. Part II: measurements on a resonant network

    NASA Astrophysics Data System (ADS)

    Guittienne, Ph; Jacquier, R.; Howling, A. A.; Furno, I.

    2015-12-01

    Measurements and analysis of a radio-frequency planar antenna are presented for applications in inductively-coupled plasma processing. The network of inductive and capacitive elements exhibits high currents under resonance which are efficient for plasma generation. Mode frequencies and impedances are accurately calculated by accounting for the mutual partial inductances using the impedance matrix. The effect of plasma inductive coupling on mode frequency shift and mode impedance is estimated using the complex image method, giving good agreement with experiment. It is proposed that the complex image method combined with the partial inductance concept (see the accompanying paper, Part I (Howling et al 2015 Plasma Sources Sci. Technol. 24 065014)) offers a general way to calculate the impedance characteristics of inductively-coupled plasma sources in planar geometry.

  2. Air-Stable Triazine-Based Ni(II) PNP Pincer Complexes As Catalysts for the Suzuki-Miyaura Cross-Coupling.

    PubMed

    Mastalir, Matthias; Stöger, Berthold; Pittenauer, Ernst; Allmaier, Günter; Kirchner, Karl

    2016-07-01

    Air-stable, thermally robust, and well-defined cationic Ni(II) PNP pincer complexes based on the 2,4-diaminotriazine scaffold are described. These complexes are active catalysts for the Suzuki-Miyaura cross-coupling of a wide range of aryl, heteroaryl (including benzoxazole, thiazole, pyridine, pyrimidine, thiazole), primary and secondary alkyl halides, and pseudohalides with different organoboronate reagents giving excellent to good isolated yields. Neutral deprotonated complexes seem to play a key role in the catalytic process. PMID:27281438

  3. A thiocyanato-bridged copper(I) cubane complex and its application in palladium-catalyzed Sonogashira coupling of aryl halides.

    PubMed

    Trivedi, Manoj; Singh, Gurmeet; Kumar, Abhinav; Rath, Nigam P

    2013-09-28

    Reaction of copper(I) thiocyanate with 1,1'-bis(di-tert-butylphosphino) ferrocene (dtbpf) in a 2:1 molar ratio in DCM-MeOH (50:50 V/V) afforded a tetranuclear copper(I) complex [Cu4(μ3-SCN)4(κ(1)-P,P-dtbpf)2] (1) with a cubane-like structure. Complex 1 was shown to be an efficient catalyst in comparison to CuI in the Sonogashira reaction. The coupling products were obtained in high yields by using Pd loadings of 0.2 mol% as well as complex-1 of 0.1 mol%. PMID:23903662

  4. The impact of ice shelf - iceberg coupling on the North Atlantic Ocean in a global climate model of intermediate complexity

    NASA Astrophysics Data System (ADS)

    Bugelmayer, M.; Roche, D. M.; Renssen, H.

    2012-04-01

    The influence of icebergs on the climate system is well known. On the one hand they act as a source of fresh water and on the other hand icebergs are a sink of latent heat. As a consequence icebergs clearly affect the ocean stratification and the formation of sea ice. The influence of icebergs on the climate system is especially important during so - called Heinrich events, which were periods with huge armadas of icebergs during the glacial climate. So far, icebergs have mostly been parameterized in global climate models as freshwater and heat fluxes. More recently, an iceberg module was used to generate bergs at specific locations. In this study a version of the Earth System Model of Intermediate Complexity, LOVECLIM, that includes a 3D dynamic - thermodynamic iceberg module (Jongma et al, 2008) is coupled to the Grenoble model for ice shelves and land ice (GRISLI, Ritz et al, 1997; 2001). Therefore, the icebergs are generated according to the amount of mass loss at the calving sites of GRISLI. The ice shelf model itself depends on the precipitation and temperature that is calculated by LOVECLIM. The calving rate of GRISLI is given back to the dynamic iceberg module in the form of an ice volume flux. The volume flux is taken to generate icebergs according to the size and mass distribution of Bigg et al. (1997). These bergs are then released at the same locations as the calving took place. In the present study we analyse the effect of moving icebergs on sea surface temperature, salinity and convection in comparison to an experiment where the ice volume that is lost by calving is given to the ocean directly as a freshwater flux at the calving site. Moreover, the influence of the start position of the icebergs on their tracks and on the ocean is investigated as we examine the differences between a model run using prescribed locations and the model run with the coupled ice shelf - iceberg model. All the experiments are done under preindustrial forcing.

  5. Variation of Exciton-Vibrational Coupling in Photosystem II Core Complexes from Thermosynechococcus elongatus As Revealed by Single-Molecule Spectroscopy

    PubMed Central

    2015-01-01

    The spectral properties and dynamics of the fluorescence emission of photosystem II core complexes are investigated by single-molecule spectroscopy at 1.6 K. The emission spectra are dominated by sharp zero-phonon lines (ZPLs). The sharp ZPLs are the result of weak to intermediate exciton-vibrational coupling and slow spectral diffusion. For several data sets, it is possible to surpass the effect of spectral diffusion by applying a shifting algorithm. The increased signal-to-noise ratio enables us to determine the exciton-vibrational coupling strength (Huang–Rhys factor) with high precision. The Huang–Rhys factors vary between 0.03 and 0.8. The values of the Huang–Rhys factors show no obvious correlation between coupling strength and wavelength position. From this result, we conclude that electrostatic rather than exchange or dispersive interactions are the main contributors to the exciton-vibrational coupling in this system. PMID:25708355

  6. Manipulating Nonlinear Emission and Cooperative Effect of CdSe/ZnS Quantum Dots by Coupling to a Silver Nanorod Complex Cavity

    PubMed Central

    Nan, Fan; Cheng, Zi-Qiang; Wang, Ya-Lan; Zhang, Qing; Zhou, Li; Yang, Zhong-Jian; Zhong, Yu-Ting; Liang, Shan; Xiong, Qihua; Wang, Qu-Quan

    2014-01-01

    Colloidal semiconductor quantum dots have three-dimensional confined excitons with large optical oscillator strength and gain. The surface plasmons of metallic nanostructures offer an efficient tool to enhance exciton-exciton coupling and excitation energy transfer at appropriate geometric arrangement. Here, we report plasmon-mediated cooperative emissions of approximately one monolayer of ensemble CdSe/ZnS quantum dots coupled with silver nanorod complex cavities at room temperature. Power-dependent spectral shifting, narrowing, modulation, and amplification are demonstrated by adjusting longitudinal surface plasmon resonance of silver nanorods, reflectivity and phase shift of silver nanostructured film, and mode spacing of the complex cavity. The underlying physical mechanism of the nonlinear excitation energy transfer and nonlinear emissions are further investigated and discussed by using time-resolved photoluminescence and finite-difference time-domain numerical simulations. Our results suggest effective strategies to design active plasmonic complex cavities for cooperative emission nanodevices based on semiconductor quantum dots. PMID:24787617

  7. Structural Model of Ligand-G Protein-coupled Receptor (GPCR) Complex Based on Experimental Double Mutant Cycle Data

    PubMed Central

    Marquer, Catherine; Fruchart-Gaillard, Carole; Letellier, Guillaume; Marcon, Elodie; Mourier, Gilles; Zinn-Justin, Sophie; Ménez, André; Servent, Denis; Gilquin, Bernard

    2011-01-01

    The snake toxin MT7 is a potent and specific allosteric modulator of the human M1 muscarinic receptor (hM1). We previously characterized by mutagenesis experiments the functional determinants of the MT7-hM1 receptor interaction (Fruchart-Gaillard, C., Mourier, G., Marquer, C., Stura, E., Birdsall, N. J., and Servent, D. (2008) Mol. Pharmacol. 74, 1554–1563) and more recently collected evidence indicating that MT7 may bind to a dimeric form of hM1 (Marquer, C., Fruchart-Gaillard, C., Mourier, G., Grandjean, O., Girard, E., le Maire, M., Brown, S., and Servent, D. (2010) Biol. Cell 102, 409–420). To structurally characterize the MT7-hM1 complex, we adopted a strategy combining double mutant cycle experiments and molecular modeling calculations. First, thirty-three ligand-receptor proximities were identified from the analysis of sixty-one double mutant binding affinities. Several toxin residues that are more than 25 Å apart still contact the same residues on the receptor. As a consequence, attempts to satisfy all the restraints by docking the toxin onto a single receptor failed. The toxin was then positioned onto two receptors during five independent flexible docking simulations. The different possible ligand and receptor extracellular loop conformations were described by performing simulations in explicit solvent. All the docking calculations converged to the same conformation of the MT7-hM1 dimer complex, satisfying the experimental restraints and in which (i) the toxin interacts with the extracellular side of the receptor, (ii) the tips of MT7 loops II and III contact one hM1 protomer, whereas the tip of loop I binds to the other protomer, and (iii) the hM1 dimeric interface involves the transmembrane helices TM6 and TM7. These results structurally support the high affinity and selectivity of the MT7-hM1 interaction and highlight the atypical mode of interaction of this allosteric ligand on its G protein-coupled receptor target. PMID:21685390

  8. Rapid and sensitive hormonal profiling of complex plant samples by liquid chromatography coupled to electrospray ionization tandem mass spectrometry

    PubMed Central

    2011-01-01

    Background Plant hormones play a pivotal role in several physiological processes during a plant's life cycle, from germination to senescence, and the determination of endogenous concentrations of hormones is essential to elucidate the role of a particular hormone in any physiological process. Availability of a sensitive and rapid method to quantify multiple classes of hormones simultaneously will greatly facilitate the investigation of signaling networks in controlling specific developmental pathways and physiological responses. Due to the presence of hormones at very low concentrations in plant tissues (10-9 M to 10-6 M) and their different chemistries, the development of a high-throughput and comprehensive method for the determination of hormones is challenging. Results The present work reports a rapid, specific and sensitive method using ultrahigh-performance liquid chromatography coupled to electrospray ionization tandem spectrometry (UPLC/ESI-MS/MS) to analyze quantitatively the major hormones found in plant tissues within six minutes, including auxins, cytokinins, gibberellins, abscisic acid, 1-amino-cyclopropane-1-carboxyic acid (the ethylene precursor), jasmonic acid and salicylic acid. Sample preparation, extraction procedures and UPLC-MS/MS conditions were optimized for the determination of all plant hormones and are summarized in a schematic extraction diagram for the analysis of small amounts of plant material without time-consuming additional steps such as purification, sample drying or re-suspension. Conclusions This new method is applicable to the analysis of dynamic changes in endogenous concentrations of hormones to study plant developmental processes or plant responses to biotic and abiotic stresses in complex tissues. An example is shown in which a hormone profiling is obtained from leaves of plants exposed to salt stress in the aromatic plant, Rosmarinus officinalis. PMID:22098763

  9. Cell-free synthesis of a functional G protein-coupled receptor complexed with nanometer scale bilayer discs

    PubMed Central

    2011-01-01

    Background G protein coupled receptors (GPCRs) represent the largest family of membrane proteins in the human genome and the richest source of targets for the pharmaceutical industry. A major limitation to characterizing GPCRs has been the difficulty in developing high-level heterologous expression systems that are cost effective. Reasons for these difficulties include inefficient transport and insertion in the plasma membrane and cytotoxicity. Additionally, GPCR purification requires detergents, which have a negative effect on receptor yields and stability. Results Here we report a detergent-free cell-free protein expression-based method to obtain pharmacologically active GPCRs in about 2 hours. Our strategy relies on the co-translational insertion of modified GPCRs into nanometer-sized planar membranes. As a model we employed an engineered β2-adrenergic receptor in which the third intracellular loop has been replaced with T4 lysozyme (β2AR -T4L). We demonstrated that nanolipoprotein particles (NLPs) are necessary for expression of active β2AR -T4L in cell-free systems. The binding specificity of the NLP- β2AR-T4L complex has been determined by competitive assays. Our results demonstrate that β2AR-T4L synthesized in vitro depends on similar oxidative conditions as those required by an in vivo-expressed receptor. Conclusions Although the activation of β2AR-T4L requires the insertion of the T4 lysozyme sequence and the yield of that active protein limited, our results conceptually prove that cell-free protein expression could be used as a fast approach to express these valuable and notoriously difficult-to-express proteins. PMID:21605442

  10. Copper(II) and nickel(II) complexes of beta-aminoketoxime ligand: syntheses, crystal structures, magnetism, and nickel(II) templated coupling of oxime with nitrile.

    PubMed

    Das, Oindrila; Adarsh, N N; Paul, Ankan; Paine, Tapan Kanti

    2010-01-18

    The syntheses, molecular structures, and magnetic properties of a dicopper(II) complex, [Cu(2)(HL(1))(2)](ClO(4))(2) (1), and its nickel(II) analog, [Ni(2)(HL(1))(2)](ClO(4))(2) (2), of a beta-amino ketoxime ligand (H(2)L(1) = 4,4,9,9-tetramethyl-5,8-diazadodecane-2,11-dione dioxime) are discussed. The metal centers in out-of-plane oximate bridged dinuclear complexes (1 and 2) display distorted trigonal bipyramidal geometry and form a six-membered M(2)(NO)(2) ring oriented in a boat conformation. The two copper(II) centers in 1 interact ferromagnetically giving rise to a triplet-spin ground state whereas the two nickel(II) centers in 2 interact antiferromagnetically to stabilize a singlet-spin state. Variable temperature magnetic susceptibility measurements establish the presence of a weak ferromagnetic coupling (J = 13 cm(-1)) in 1 and a weak anitiferromagnetic coupling (J = -12 cm(-1)) in 2. The exchange coupling constant derived from B3LYP computations in conjunction with broken symmetry spin-projection techniques for the oximate bridged dinuclear copper(II) complex shows excellent agreement with the corresponding experimental value. A square-planar mononuclear nickel(II) complex of the dioxime ligand, [Ni(H(2)L(1))](ClO(4))(2) (3), is reported along with its crystal structure, which reacts with acetonitrile to produce a six-coordinate mononuclear complex, [Ni(L(2))](ClO(4))(2) (4). The ligand (L(2)) in complex 4 is the iminoacyl derivative of oxime, where the coupling of oxime and acetonitrile takes place via a proton-assisted pathway. The iminoacylation of H(2)L(1) works with other nitriles like butyronitrile and benzonitrile. Computational studies support a proton-assisted coupling of oxime with nitrile. The critical transition states have been located for the iminoacylation reaction. Complex 4 can be converted back to complex 3 by reacting with sodium acetate in methanol. PMID:20025254

  11. The copper-free Sonogashira cross-coupling reaction promoted by palladium complexes of nitrogen-containing chelating ligands in neat water at room temperature.

    PubMed

    Zhong, Hong; Wang, Jinyun; Li, Liuyi; Wang, Ruihu

    2014-02-01

    The commercially available 2,2'-dipyridylamine was used as a supporting ligand in the palladium-catalyzed Sonogashira cross-coupling reaction. The reactions between aryl iodides and terminal alkynes with different steric hindrance can be efficiently performed in the absence of copper in neat water at room temperature. The superior catalytic performance of the catalytic system was attributed to water solubility of the palladium 2,2'-dipyridylamine complex. Palladium nanoparticles with small size and narrow size distribution were formed after the cross-coupling reaction. PMID:24281778

  12. Half-sandwich nickel complexes with ring-expanded NHC ligands - synthesis, structure and catalytic activity in Kumada-Tamao-Corriu coupling.

    PubMed

    Banach, Ł; Guńka, P A; Buchowicz, W

    2016-06-01

    The general synthesis of [Ni(Cp)(X)(NHC)] complexes from a nickel halide, CpLi, and a carbene solution is reported. This procedure yields unprecedented complexes with ring-expanded NHC ligands (RE-NHC) of six- (1a, 1b), seven- (1c), and eight-membered (1d) heterocycles. The NMR spectra of 1a-1d are consistent with the hindered rotation of Ni-Ccarbene and N-CMes bonds, while X-ray analyses of 1b, 1c, and 1d reveal a pronounced trans influence of the RE-NHC ligands. Complexes 1a-1e are efficient pre-catalysts in Kumada-Tamao-Corriu coupling with the maximum efficiency observed for complexes bearing the six-membered NHC. PMID:26853761

  13. First high-power model of the annular-ring coupled structure for use in the Japan Proton Accelerator Research Complex linac

    NASA Astrophysics Data System (ADS)

    Ao, Hiroyuki; Yamazaki, Yoshishige

    2012-01-01

    A prototype cavity for the annular-ring coupled structure (ACS) for use in the Japan Proton Accelerator Research Complex (J-PARC) linac has been developed to confirm the feasibility of achieving the required performance. This prototype cavity is a buncher module, which includes ten accelerating cells in total. The ACS cavity is formed by the silver brazing of ACS half-cell pieces stacked in a vacuum furnace. The accelerating cell of the ACS is surrounded by a coupling cell. We, therefore, tuned the frequencies of the accelerating and coupling cells by an ultraprecision lathe before brazing, taking into account the frequency shift due to brazing. The prototype buncher module was successfully conditioned up to 600 kW, which corresponds to an accelerating field that is higher than the designed field of 4.1MV/m by 30%. We describe the frequency-tuning results for the prototype buncher module and its high-power conditioning.

  14. Reconstitution of photosynthetic energy conservation. II. Photophosphorylation in liposomes containing photosystem-I reaction center and chloroplast coupling-factor complex.

    PubMed

    Hauska, G; Samoray, D; Orlich, G; Nelson, N

    1980-10-01

    Photophosphorylation has been reconstituted in a liposomal system containing reaction centers of photosystem I and coupling-factor complex, both highly purified from spinach chloroplasts. This energy-converting model system was put together by diluting the preparation of the coupling-factor complex with an aqueous suspension of proteolipid vesicles, preformed from photosystem-I reaction centers and soybean phospholipids by sonication. In the presence of reduced N-methyl-phenazonium methosulfate the system catalyzed photophosphorylation with rates up to 50 mumol ATP formed x mg chlorophyll-1 x h-1, which was sensitive to uncouplers and to N,N'-dicyclohexyl-carbodiimide. The properties of the system in comparison to chloroplasts is discussed. PMID:6450680

  15. Palladium(II)-1-phenylthio-2-arylchalcogenoethane complexes: palladium phosphide nano-peanut and ribbon formation controlled by chalcogen and Suzuki coupling activation.

    PubMed

    Kumar Rao, Gyandshwar; Kumar, Arun; Saleem, Fariha; Singh, Mahabir P; Kumar, Satyendra; Kumar, Bharat; Mukherjee, Goutam; Singh, Ajai K

    2015-04-14

    The ligands PhSCH2CH2EAr (; E = S, Se or Te) and their Pd-complexes [PdLCl2] () have been synthesized and authenticated with their (1)H, (13)C{(1)H}, (77)Se{(1)H} and (125)Te{(1)H} NMR spectra. Single crystal structures of and reveal the geometry of donor atoms around palladium as nearly square planar. Thermolysis of all three complexes in trioctylphosphine (TOP) at 350, 320 and 280 °C, respectively, results in a single phase of crystalline PdP2. The morphology of the phase varies with 'E' to some extent. The nanopeanuts (size ∼30 and ∼35 nm) were formed with and as precursor complexes. On using complex as a precursor nanoribbons are formed. The preferential growth in the (202) plane in the case of all the three precursor complexes has been rationalized in terms of texture coefficient and average crystallite size. All three complexes and PdP2 NPs have been explored for Suzuki-Miyaura coupling of several aryl halides. Complexes and show good catalytic activity but complex does not. The activity appears to result due to in situ generated palladium containing nanoparticles (NPs) in the case of and . The formation of inactive large Pd aggregates in the case of appears to be responsible for the difference. The PdP2 NPs have been found to show good catalytic activity and recyclability up to six reaction cycles. The results of the three phase test suggest the involvement of both homogeneous and heterogeneous pathways in the activation of Suzuki coupling. DFT based free energy calculations are consistent with the results of catalysis via Pd(0) protected with the ligand. This palladium may also be released from in situ generated NPs. In the case of , negligible reactivity may be due to non-release of Pd. PMID:25757704

  16. Aspects of Subunit Interactions in the Chloroplast ATP Synthase (I. Isolation of a Chloroplast Coupling Factor 1-Subunit III Complex from Spinach Thylakoids).

    PubMed Central

    Wetzel, C. M.; McCarty, R. E.

    1993-01-01

    A chloroplast ATP synthase complex (CF1 [chloroplast-coupling factor 1]-CF0 [membrane-spanning portion of chloroplast ATP synthase]) depleted of all CF0 subunits except subunit III (also known as the proteolipid subunit) was purified to study the interaction between CF1 and subunit III. Subunit III has a putative role in proton translocation across the thylakoid membrane during photophosphorylation; therefore, an accurate model of subunit inter-actions involving subunit III will be valuable for elucidating the mechanism and regulation of energy coupling. Purification of the complex from a crude CF1-CF0 preparation from spinach (Spinacia oleracea) thylakoids was accomplished by detergent treatment during anion-exchange chromatography. Subunit III in the complex was positively identified by amino acid analysis and N-terminal sequencing. The association of subunit III with CF1 was verified by linear sucrose gradient centrifugation, immunoprecipitation, and incorporation of the complex into asolectin liposomes. After incorporation into liposomes, CF1 was removed from the CF1-III complex by ethylenediaminetetracetate treatment. The subunit III-proteoliposomes were competent to rebind purified CF1. These results indicate that subunit III directly interacts with CF1 in spinach thylakoids. PMID:12231815

  17. Intramolecular transfer of {open_quotes}CO{close_quotes} from ({eta}{sup 6}-arene)Cr(CO){sub 3} complexes in stille-type palladium-catalyzed cross coupling reactions

    SciTech Connect

    Caldirola, P.; Chowdhury, R.; Johansson, A.M.; Hacksell, U.

    1995-12-31

    The reaction between [{eta}{sup 6}-(trialkylstannyl)benzene]Cr(CO){sub 3} complexes and different electrophiles such as iodobenzene and aryltriflate and the coupling between (tributylphenyl)stannane and the Cr(CO){sub 3} complex of chlorobenzene have been studied. Products from two different types of reactions were observed: (1) benzophenone along with the alkylarylketone, resulting from a carbonylative coupling, and (2) biphenyl, arising from a direct coupling.

  18. Decarboxylative Coupling Reaction in ESI(-)-MS/MS of 4-Nitrobenzyl 4-Hydroxybenzoates: Triplet Ion-Neutral Complex-Mediated 4-Nitrobenzyl Transfer

    NASA Astrophysics Data System (ADS)

    Zhang, Xiaoping; Bai, Xingfeng; Fang, Liwen; Jiang, Kezhi; Li, Zuguang

    2016-05-01

    In negative electrospray ionization mass spectrometry of 4-nitrobenzyl 4-hydroxybenzoates, a decarboxylation reaction, which was significantly promoted by the presence of a nitro group on the benzyl group, competed with radical elimination reactions. Density functional theory calculations indicated that decarboxylation of deprotonated 4-nitrobenzyl vanillate occurred via a radical route involving homolytic cleavage of the Cbenzyl-O bond to give a triplet ion-neutral complex, followed by decarboxylative coupling.

  19. Absorption Spectroscopy, Emissive Properties, and Ultrafast Intersystem Crossing Processes in Transition Metal Complexes: TD-DFT and Spin-Orbit Coupling.

    PubMed

    Daniel, Chantal

    2016-01-01

    Absorption spectroscopy, emissive properties, and ultrafast intersystem crossing processes in transition metal complexes are discussed in the light of recent developments in time-dependent density functional theory (TD-DFT), spin-orbit coupling (SOC) effects, and non-adiabatic excited states dynamics. Methodological highlights focus on spin-orbit and vibronic couplings and on the recent strategies available for simulating ultra-fast intersystem crossings (ISC).The role of SOC in the absorption spectroscopy of third-row transition metal complexes is illustrated by two cases studies, namely Ir(III) phenyl pyridine and Re(I) carbonyl bipyridine complexes.The problem of luminescence decay in third-row transition metal complexes handled by TD-DFT linear and quadratic response theories including SOC is exemplified by three studies: (1) the phosphorescence of Ir(III) complexes from the lowest triplet state; (2) the emissive properties of square planar Pt(II) complexes with bidentate and terdentate ligands characterized by low-lying metal-to-ligand-charge-transfer (MLCT) and metal-centered (MC) states; and (3) the ultra-fast luminescence decay of Re(I) carbonyl bipyridine halides via low-lying singlet and triplet charge transfer states delocalized over the bipyridine and the halide ligands.Ultrafast ISC occurring in spin crossover [Fe (bpy)3]2+, in [Ru (bpy)3]2+, and [Re (Br)(CO)3(bpy] complexes are deciphered thanks to recent developments based on various approaches, namely non-radiative rate theory within the Condon approximation, non-adiabatic surface hopping molecular dynamics, and quantum wave packet dynamics propagation. PMID:26129697

  20. The role of complex networks in behavior epidemiology. Comment on "Coupled disease-behavior dynamics on complex networks: A review" by Z. Wang et al.

    NASA Astrophysics Data System (ADS)

    Zhao, Dawei; Wang, Lianhai

    2015-12-01

    Outbreaks of disease can trigger spontaneous behavioral response of individuals to consider prevention measures (mainly including medical cure and non-pharmaceutical intervention), which usually in turn influence the diffusion of epidemic, namely, forming the interplay between individual behaviors and epidemic dynamics. During the past decade, understanding such coupled disease-behavior dynamics in population has become a critical tool for predicting the disease evolution and designing effective prevention strategies [1-3].

  1. An Annular Lipid Belt Is Essential for Allosteric Coupling and Viral Inhibition of the Antigen Translocation Complex TAP (Transporter Associated with Antigen Processing)*

    PubMed Central

    Eggensperger, Sabine; Fisette, Olivier; Parcej, David; Schäfer, Lars V.; Tampé, Robert

    2014-01-01

    The transporter associated with antigen processing (TAP) constitutes a focal element in the adaptive immune response against infected or malignantly transformed cells. TAP shuttles proteasomal degradation products into the lumen of the endoplasmic reticulum for loading of major histocompatibility complex (MHC) class I molecules. Here, the heterodimeric TAP complex was purified and reconstituted in nanodiscs in defined stoichiometry. We demonstrate that a single heterodimeric core-TAP complex is active in peptide binding, which is tightly coupled to ATP hydrolysis. Notably, with increasing peptide length, the ATP turnover was gradually decreased, revealing that ATP hydrolysis is coupled to the movement of peptide through the ATP-binding cassette transporter. In addition, all-atom molecular dynamics simulations show that the observed 22 lipids are sufficient to form an annular belt surrounding the TAP complex. This lipid belt is essential for high affinity inhibition by the herpesvirus immune evasin ICP47. In conclusion, nanodiscs are a powerful approach to study the important role of lipids as well as the function, interaction, and modulation of the antigen translocation machinery. PMID:25305015

  2. Spatial modulation of light transmission through a single microcavity by coupling of photosynthetic complex excitations to surface plasmons

    NASA Astrophysics Data System (ADS)

    Carmeli, Itai; Cohen, Moshik; Heifler, Omri; Lilach, Yigal; Zalevsky, Zeev; Mujica, Vladimiro; Richter, Shachar

    2015-06-01

    Molecule-plasmon interactions have been shown to have a definite role in light propagation through optical microcavities due to strong coupling between molecular excitations and surface plasmons. This coupling can lead to macroscopic extended coherent states exhibiting increment in temporal and spatial coherency and a large Rabi splitting. Here, we demonstrate spatial modulation of light transmission through a single microcavity patterned on a free-standing Au film, strongly coupled to one of the most efficient energy transfer photosynthetic proteins in nature, photosystem I. Here we observe a clear correlation between the appearance of spatial modulation of light and molecular photon absorption, accompanied by a 13-fold enhancement in light transmission and the emergence of a distinct electromagnetic standing wave pattern in the cavity. This study provides the path for engineering various types of bio-photonic devices based on the vast diversity of biological molecules in nature.

  3. The order O({α}_t{α}_s) corrections to the trilinear Higgs self-couplings in the complex NMSSM

    NASA Astrophysics Data System (ADS)

    Mühlleitner, Margarete; Nhung, Dao Thi; Ziesche, Hanna

    2015-12-01

    A consistent interpretation of the Higgs data requires the same precision in the Higgs boson masses and in the trilinear Higgs self-couplings, which are related through their common origin from the Higgs potential. In this work we provide the two-loop corrections at O({α}_t{α}_s) in the approximation of vanishing external momenta to the trilinear Higgs self-couplings in the CP-violating Next-to-Minimal Supersymmetric extension of the Standard Model (NMSSM). In the top/stop sector two different renormalization schemes have been implemented, the OS and the overline{DR} scheme. The two-loop corrections to the self-couplings are of the order of 10% in the investigated scenarios. The theoretical error, estimated both from the variation of the renormalization scale and from the change of the top/stop sector renormalization scheme, has been shown to be reduced due to the inclusion of the two-loop corrections.

  4. Radical Monocationic Guanidino-Functionalized Aromatic Compounds (GFAs) as Bridging Ligands in Dinuclear Metal Acetate Complexes: Synthesis, Electronic Structure, and Magnetic Coupling.

    PubMed

    Eberle, Benjamin; Damjanović, Marko; Enders, Markus; Leingang, Simone; Pfisterer, Jessica; Krämer, Christoph; Hübner, Olaf; Kaifer, Elisabeth; Himmel, Hans-Jörg

    2016-02-15

    In this work, the oxidation of several new dinuclear metal (M) acetate complexes of the redox-active guanidino-functionalized aromatic compound (GFA) 1,2,4,5-tetrakis(tetramethylguanidino)benzene (1) was studied. The complexes [1{M(OAc)2}2] (M = Ni or Pd) were oxidized to the radical monocationic complexes [1{M(OAc)2}2](+ •). From CV (cyclic voltammetry) measurements, the Gibbs free enthalpy for disproportionation of [1{M(OAc)2}2](+ •) into [1{M(OAc)2}2] and [1{M(OAc)2}2](2+) could be estimated to be roughly +20 kJ mol(-1) in CH2Cl2 solution. A characteristic feature of the [1{M(OAc)2}2](+ •) complexes is the presence of intense metal-ligand charge-transfer bands in the electronic absorption spectra. The complex [1{Ni(OAc)2}2](+ •) combines three paramagnetic centers with four metal-centered unpaired electrons and a ligand centered π-radical and exhibits a sextet electronic ground state. Spin distribution of the Ni complexes was evaluated by paramagnetic (1)H and (13)C NMR and was correlated with calculations. The strong ferromagnetic metal-ligand magnetic coupling was studied in the solid state by magnetometric (SQUID) measurements and by quantum chemical (DFT) calculations. The temperature dependence of the paramagnetic NMR shift was used for the evaluation of the magnetic coupling between the Ni centers and the π-radical in solution. PMID:26814470

  5. Distance-Independent Charge Recombination Kinetics in Cytochrome c - Cytochrome c Peroxidase Complexes: Compensating Changes in the Electronic Coupling and Reorganization Energies

    PubMed Central

    Jiang, Nan; Kuznetsov, Aleksey; Nocek, Judith M.; Hoffman, Brian M.; Crane, Brian R.; Hu, Xiangqian; Beratan, David N.

    2013-01-01

    Charge recombination rate constants vary no more than three-fold for inter-protein ET in the Zn-substituted wild type (WT) cytochrome c peroxidase (CcP):cytochrome c (Cc) complex and in complexes with four mutants of the Cc protein (i.e., F82S, F82W, F82Y and F82I), despite large differences in the ET distance. Theoretical analysis indicates that charge recombination for all complexes involves a combination of tunneling and hopping via Trp191. For three of the five structures (WT and F82S(W)), the protein favors hopping more than that in the other two structures that have longer heme→ZnP distances (F82Y(I)). Experimentally observed biexponential ET kinetics is explained by the complex locking in alternative coupling pathways, where the acceptor hole state is either primarily localized on ZnP (slow phase) or on Trp191 (fast phase). The large conformational differences between the CcP:Cc interface for the F82Y(I) mutants compared to the WT and F82S(W) complexes are predicted to change the reorganization energies for the CcP:Cc ET reactions because of changes in solvent exposure and inter-protein ET distances. Since the recombination reaction is likely to occur in the inverted Marcus regime, an increased reorganization energy compensates the decreased role for hopping recombination (and the longer transfer distance) in the F82Y(I) mutants. Taken together, coupling pathway and reorganization energy effects for the five protein complexes explains the observed insensitivity of recombination kinetics to donor-acceptor distance and docking pose and also reveals how hopping through aromatic residues can accelerate long-range ET. PMID:23895339

  6. Analytical developments for the determination of monomethylmercury complexes with low molecular mass thiols by reverse phase liquid chromatography hyphenated to inductively coupled plasma mass spectrometry.

    PubMed

    Bouchet, Sylvain; Björn, Erik

    2014-04-25

    The behavior of monomethylmercury (MMHg) is markedly influenced by its distribution among complexes with low molecular mass (LMM) thiols but analytical methodologies dedicated to measure such complexes are very scarce up to date. In this work, we selected 15 LMM thiols often encountered in living organisms and/or in the environment and evaluated the separation of the 15 corresponding MMHg-thiol complexes by various high performance liquid chromatography (HPLC) columns. Two C18 (Phenomenex Synergi Hydro-RP and LunaC18(2)), two phenyl (Inertsil Ph 3 and 5μm) and one mixed-mode (Restek Ultra IBD) stationary phases were tested for their retention and resolution capacities of the various complexes. The objective was to find simple separation conditions with low organic contents in the mobile phase to provide optimal conditions for detection by inductively coupled plasma mass spectrometry (ICPMS). The 15 complexes were synthesized in solution and characterized by electrospray ionization-mass spectrometry (ESI-MS). The C18 columns tested were either not resolutive enough or too retentive. The 3μm phenyl stationary phase was able to resolve 10 out of the 15 complexes in less than 25min, under isocratic conditions. The mixed-mode column was especially effective at separating the most hydrophilic complexes (6 complexes out of the 15), corresponding to the main LMM thiols found in living organisms. The detection limits (DLs) for these two columns were in the low nanomolar range and overall slightly better for the phenyl column. The possibilities offered by such methodology were exemplified by monitoring the time-course concentrations of four MMHg-thiol complexes within a phytoplankton incubation containing MMHg in the presence of an excess of four added thiols. PMID:24657146

  7. Inventory of metal complexes circulating in plant fluids: a reliable method based on HPLC coupled with dual elemental and high-resolution molecular mass spectrometric detection.

    PubMed

    Flis, Paulina; Ouerdane, Laurent; Grillet, Louis; Curie, Catherine; Mari, Stéphane; Lobinski, Ryszard

    2016-08-01

    Description of metal species in plant fluids such as xylem, phloem or related saps remains a complex challenge usually addressed either by liquid chromatography-mass spectrometry, X-ray analysis or computational prediction. To date, none of these techniques has achieved a complete and true picture of metal-containing species in plant fluids, especially for the least concentrated complexes. Here, we present a generic analytical methodology for a large-scale (> 10 metals, > 50 metal complexes) detection, identification and semiquantitative determination of metal complexes in the xylem and embryo sac liquid of the green pea, Pisum sativum. The procedure is based on direct injection using hydrophilic interaction chromatography with dual detection by elemental (inductively coupled plasma mass spectrometry) and molecular (high-resolution electrospray mass spectrometry) mass spectrometric detection. Numerous and novel complexes of iron(II), iron(III), copper(II), zinc, manganese, cobalt(II), cobalt(III), magnesium, calcium, nickel and molybdenum(IV) with several ligands including nicotianamine, citrate, malate, histidine, glutamine, aspartic acid, asparagine, phenylalanine and others are observed in pea fluids and discussed. This methodology provides a large inventory of various types of metal complexes, which is a significant asset for future biochemical and genetic studies into metal transport/homeostasis. PMID:27111838

  8. Public health impact of disease-behavior dynamics. Comment on "Coupled disease-behavior dynamics on complex networks: A review" by Z. Wang et al.

    NASA Astrophysics Data System (ADS)

    Wells, Chad R.; Galvani, Alison P.

    2015-12-01

    In a loop of dynamic feedback, behavior such as the decision to vaccinate, hand washing, or avoidance influences the progression of the epidemic, yet behavior is driven by the individual's and population's perceived risk of infection during an outbreak. In what we believe will become a seminal paper that stimulates future research as well as an informative teaching aid, Wang et. al. comprehensively review methodological advances that have been used to incorporate human behavior into epidemiological models on the effects of coupling disease transmission and behavior on complex social networks [1]. As illustrated by the recent outbreaks of measles and Middle Eastern Respiratory Syndrome (MERS), here we highlight the importance of coupling behavior and disease transmission that Wang et al. address.

  9. Accessing Molecularly Complex Azaborines: Palladium-Catalyzed Suzuki–Miyaura Cross-Couplings of Brominated 2,1-Borazaronaphthalenes and Potassium Organotrifluoroborates

    PubMed Central

    2015-01-01

    Despite their potential applications in both medicinal chemistry and materials science, there have been limited reports on the functionalization of 2,1-borazaronaphthalenes since their discovery in 1959. To access new chemical space and build molecular complexity, the Suzuki–Miyaura cross-coupling of brominated 2,1-borazaronaphthalenes has been investigated. The palladium-catalyzed cross-coupling proceeds with an array of potassium (hetero)aryltrifluoroborates in high yield with low catalyst loadings under mild reaction conditions. By the use of a high-yielding bromination of various 2,1-borazaronaphthalenes to generate electrophilic azaborine species, a library of 3-(hetero)aryl and 3,6-diaryl-2,1-borazaronaphthalenes has been synthesized. PMID:24984003

  10. Modelling real disease dynamics with behaviourally adaptive complex networks. Comment on "Coupled disease-behavior dynamics on complex networks: A review" by Z. Wang et al.

    NASA Astrophysics Data System (ADS)

    Small, Michael

    2015-12-01

    Mean field compartmental models of disease transmission have been successfully applied to a host of different scenarios, and the Kermack-McKendrick equations are now a staple of mathematical biology text books. In Susceptible-Infected-Removed format these equations provide three coupled first order ordinary differential equations with a very mild nonlinearity and they are very well understood. However, underpinning these equations are two important assumptions: that the population is (a) homogeneous, and (b) well-mixed. These assumptions become closest to being true for diseases infecting a large portion of the population for which inevitable individual effects can be averaged away. Emerging infectious disease (such as, in recent times, SARS, avian influenza, swine flu and ebola) typically does not conform to this scenario. Individual contacts and peculiarities of the transmission network play a vital role in understanding the dynamics of such relatively rare infections - particularly during the early stages of an outbreak.