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Sample records for information transfer complexity

  1. Thermodynamic aspects of information transfer in complex dynamical systems.

    PubMed

    Cafaro, Carlo; Ali, Sean Alan; Giffin, Adom

    2016-02-01

    From the Horowitz-Esposito stochastic thermodynamical description of information flows in dynamical systems [J. M. Horowitz and M. Esposito, Phys. Rev. X 4, 031015 (2014)], it is known that while the second law of thermodynamics is satisfied by a joint system, the entropic balance for the subsystems is adjusted by a term related to the mutual information exchange rate between the two subsystems. In this article, we present a quantitative discussion of the conceptual link between the Horowitz-Esposito analysis and the Liang-Kleeman work on information transfer between dynamical system components [X. S. Liang and R. Kleeman, Phys. Rev. Lett. 95, 244101 (2005)]. In particular, the entropic balance arguments employed in the two approaches are compared. Notwithstanding all differences between the two formalisms, our work strengthens the Liang-Kleeman heuristic balance reasoning by showing its formal analogy with the recent Horowitz-Esposito thermodynamic balance arguments. PMID:26986295

  2. Thermodynamic aspects of information transfer in complex dynamical systems

    NASA Astrophysics Data System (ADS)

    Cafaro, Carlo; Ali, Sean Alan; Giffin, Adom

    2016-02-01

    From the Horowitz-Esposito stochastic thermodynamical description of information flows in dynamical systems [J. M. Horowitz and M. Esposito, Phys. Rev. X 4, 031015 (2014), 10.1103/PhysRevX.4.031015], it is known that while the second law of thermodynamics is satisfied by a joint system, the entropic balance for the subsystems is adjusted by a term related to the mutual information exchange rate between the two subsystems. In this article, we present a quantitative discussion of the conceptual link between the Horowitz-Esposito analysis and the Liang-Kleeman work on information transfer between dynamical system components [X. S. Liang and R. Kleeman, Phys. Rev. Lett. 95, 244101 (2005), 10.1103/PhysRevLett.95.244101]. In particular, the entropic balance arguments employed in the two approaches are compared. Notwithstanding all differences between the two formalisms, our work strengthens the Liang-Kleeman heuristic balance reasoning by showing its formal analogy with the recent Horowitz-Esposito thermodynamic balance arguments.

  3. Efficiency of informational transfer in regular and complex networks

    NASA Astrophysics Data System (ADS)

    Vragović, I.; Louis, E.; Díaz-Guilera, A.

    2005-03-01

    We analyze the process of informational exchange through complex networks by measuring network efficiencies. Aiming to study nonclustered systems, we propose a modification of this measure on the local level. We apply this method to an extension of the class of small worlds that includes declustered networks and show that they are locally quite efficient, although their clustering coefficient is practically zero. Unweighted systems with small-world and scale-free topologies are shown to be both globally and locally efficient. Our method is also applied to characterize weighted networks. In particular we examine the properties of underground transportation systems of Madrid and Barcelona and reinterpret the results obtained for the Boston subway network.

  4. Quantifying information transfer and mediation along causal pathways in complex systems

    NASA Astrophysics Data System (ADS)

    Runge, Jakob

    2015-12-01

    Measures of information transfer have become a popular approach to analyze interactions in complex systems such as the Earth or the human brain from measured time series. Recent work has focused on causal definitions of information transfer aimed at decompositions of predictive information about a target variable, while excluding effects of common drivers and indirect influences. While common drivers clearly constitute a spurious causality, the aim of the present article is to develop measures quantifying different notions of the strength of information transfer along indirect causal paths, based on first reconstructing the multivariate causal network. Another class of novel measures quantifies to what extent different intermediate processes on causal paths contribute to an interaction mechanism to determine pathways of causal information transfer. The proposed framework complements predictive decomposition schemes by focusing more on the interaction mechanism between multiple processes. A rigorous mathematical framework allows for a clear information-theoretic interpretation that can also be related to the underlying dynamics as proven for certain classes of processes. Generally, however, estimates of information transfer remain hard to interpret for nonlinearly intertwined complex systems. But if experiments or mathematical models are not available, then measuring pathways of information transfer within the causal dependency structure allows at least for an abstraction of the dynamics. The measures are illustrated on a climatological example to disentangle pathways of atmospheric flow over Europe.

  5. Quantifying information transfer and mediation along causal pathways in complex systems.

    PubMed

    Runge, Jakob

    2015-12-01

    Measures of information transfer have become a popular approach to analyze interactions in complex systems such as the Earth or the human brain from measured time series. Recent work has focused on causal definitions of information transfer aimed at decompositions of predictive information about a target variable, while excluding effects of common drivers and indirect influences. While common drivers clearly constitute a spurious causality, the aim of the present article is to develop measures quantifying different notions of the strength of information transfer along indirect causal paths, based on first reconstructing the multivariate causal network. Another class of novel measures quantifies to what extent different intermediate processes on causal paths contribute to an interaction mechanism to determine pathways of causal information transfer. The proposed framework complements predictive decomposition schemes by focusing more on the interaction mechanism between multiple processes. A rigorous mathematical framework allows for a clear information-theoretic interpretation that can also be related to the underlying dynamics as proven for certain classes of processes. Generally, however, estimates of information transfer remain hard to interpret for nonlinearly intertwined complex systems. But if experiments or mathematical models are not available, then measuring pathways of information transfer within the causal dependency structure allows at least for an abstraction of the dynamics. The measures are illustrated on a climatological example to disentangle pathways of atmospheric flow over Europe. PMID:26764766

  6. 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.

  7. Electron transfer dissociation provides higher-order structural information of native and partially unfolded protein complexes.

    PubMed

    Lermyte, Frederik; Sobott, Frank

    2015-08-01

    Top-down sequencing approaches are becoming ever more popular for protein characterization, due to the ability to distinguish and characterize different protein isoforms. Under non-denaturing conditions, electron transfer dissociation (ETD) can furthermore provide important information on the exposed surface of proteins or complexes, thereby contributing to the characterization of their higher-order structure. Here, we investigate this approach using top-down ETD of tetrameric hemoglobin, concanavalin A, and alcohol dehydrogenase combined with ion mobility (IM) on a commercially available quadrupole/ion mobility/time-of-flight instrument (Waters Synapt G2). By applying supplemental activation in the transfer cell (post-IM), we release ETD fragments and attain good sequence coverage in the exposed terminal regions of the protein. We investigate the correlation between observed sites of fragmentation with regions of solvent accessibility, as derived from the crystal structure. Ion acceleration prior to ETD is also used to cause collision-induced unfolding (CIU) of the complexes without monomer ejection, as evidenced by the IM profiles. These partially unfolded tetramers show efficient fragmentation in some regions which are not sequenced under more gentle MS conditions. We show that by increasing CIU in small increments and monitoring the changes in the fragmentation pattern, it is possible to follow the initial steps of gas-phase protein unfolding. Fragments from partially unfolded protein complexes are released immediately after electron transfer, prior to IM (they do not share the drift time of their precursor), and observed without the need for supplemental activation. This is further evidence that the higher-order structure in these protein regions has been disrupted. PMID:26081219

  8. Symbolic local information transfer

    NASA Astrophysics Data System (ADS)

    Nakajima, K.; Haruna, T.

    2013-06-01

    Recently, the permutation-information theoretic approach has been used in a broad range of research fields. In particular, in the study of high-dimensional dynamical systems, it has been shown that this approach can be effective in characterizing global properties, including the complexity of their spatiotemporal dynamics. Here, we show that this approach can also be applied to reveal local spatiotemporal profiles of distributed computations existing at each spatiotemporal point in the system. J. T. Lizier et al. have recently introduced the concept of local information dynamics, which consists of information storage, transfer, and modification. This concept has been intensively studied with regard to cellular automata, and has provided quantitative evidence of several characteristic behaviors observed in the system. In this paper, by focusing on the local information transfer, we demonstrate that the application of the permutation-information theoretic approach, which introduces natural symbolization methods, makes the concept easily extendible to systems that have continuous states. We propose measures called symbolic local transfer entropies, and apply these measures to two test models, the coupled map lattice (CML) system and the Bak-Sneppen model (BS-model), to show their relevance to spatiotemporal systems that have continuous states. In the CML, we demonstrate that it can be successfully used as a spatiotemporal filter to stress a coherent structure buried in the system. In particular, we show that the approach can clearly stress out defect turbulences or Brownian motion of defects from the background, which gives quantitative evidence suggesting that these moving patterns are the information transfer substrate in the spatiotemporal system. We then show that these measures reveal qualitatively different properties from the conventional approach using the sliding window method, and are also robust against external noise. In the BS-model, we demonstrate that

  9. Communication complexity and information complexity

    NASA Astrophysics Data System (ADS)

    Pankratov, Denis

    Information complexity enables the use of information-theoretic tools in communication complexity theory. Prior to the results presented in this thesis, information complexity was mainly used for proving lower bounds and direct-sum theorems in the setting of communication complexity. We present three results that demonstrate new connections between information complexity and communication complexity. In the first contribution we thoroughly study the information complexity of the smallest nontrivial two-party function: the AND function. While computing the communication complexity of AND is trivial, computing its exact information complexity presents a major technical challenge. In overcoming this challenge, we reveal that information complexity gives rise to rich geometrical structures. Our analysis of information complexity relies on new analytic techniques and new characterizations of communication protocols. We also uncover a connection of information complexity to the theory of elliptic partial differential equations. Once we compute the exact information complexity of AND, we can compute exact communication complexity of several related functions on n-bit inputs with some additional technical work. Previous combinatorial and algebraic techniques could only prove bounds of the form theta( n). Interestingly, this level of precision is typical in the area of information theory, so our result demonstrates that this meta-property of precise bounds carries over to information complexity and in certain cases even to communication complexity. Our result does not only strengthen the lower bound on communication complexity of disjointness by making it more exact, but it also shows that information complexity provides the exact upper bound on communication complexity. In fact, this result is more general and applies to a whole class of communication problems. In the second contribution, we use self-reduction methods to prove strong lower bounds on the information

  10. Information Transfer in 1990.

    ERIC Educational Resources Information Center

    Hough, Roger W.

    Results of a recent study of potential demand for electronic information transfer services in 1970-1990 are presented. Projections are made for new services such as electronic mail, remote library browsing, checkless society transactions, video telephone and others, as well as conventional services such as telephone, telegraph and network program…

  11. Transfer of information in noise induced transport

    NASA Astrophysics Data System (ADS)

    Sanchez, J. R.; Arizmendi, C. M.

    1999-09-01

    Time correlated fluctuations interacting with a spatial asymmetry potential are sufficient conditions to give rise to transport of Brownian particles. The transfer of information coming from the nonequilibrium bath, viewed as a source of negentropy, give rise to the correlated noise. The algorithmic complexity of an object provides a means of quantifying its information contents. The Kolmogorov information entropy or algorithmic complexity is investigated in order to quantify the transfer of information that occurs in computational models showing noise induced transport. The complexity is measured in terms of the average number of bits per time unit necessary to specify the sequence generated by the system.

  12. Measuring Information-Transfer Delays

    PubMed Central

    Wibral, Michael; Pampu, Nicolae; Priesemann, Viola; Siebenhühner, Felix; Seiwert, Hannes; Lindner, Michael; Lizier, Joseph T.; Vicente, Raul

    2013-01-01

    In complex networks such as gene networks, traffic systems or brain circuits it is important to understand how long it takes for the different parts of the network to effectively influence one another. In the brain, for example, axonal delays between brain areas can amount to several tens of milliseconds, adding an intrinsic component to any timing-based processing of information. Inferring neural interaction delays is thus needed to interpret the information transfer revealed by any analysis of directed interactions across brain structures. However, a robust estimation of interaction delays from neural activity faces several challenges if modeling assumptions on interaction mechanisms are wrong or cannot be made. Here, we propose a robust estimator for neuronal interaction delays rooted in an information-theoretic framework, which allows a model-free exploration of interactions. In particular, we extend transfer entropy to account for delayed source-target interactions, while crucially retaining the conditioning on the embedded target state at the immediately previous time step. We prove that this particular extension is indeed guaranteed to identify interaction delays between two coupled systems and is the only relevant option in keeping with Wiener’s principle of causality. We demonstrate the performance of our approach in detecting interaction delays on finite data by numerical simulations of stochastic and deterministic processes, as well as on local field potential recordings. We also show the ability of the extended transfer entropy to detect the presence of multiple delays, as well as feedback loops. While evaluated on neuroscience data, we expect the estimator to be useful in other fields dealing with network dynamics. PMID:23468850

  13. Measuring information-transfer delays.

    PubMed

    Wibral, Michael; Pampu, Nicolae; Priesemann, Viola; Siebenhühner, Felix; Seiwert, Hannes; Lindner, Michael; Lizier, Joseph T; Vicente, Raul

    2013-01-01

    In complex networks such as gene networks, traffic systems or brain circuits it is important to understand how long it takes for the different parts of the network to effectively influence one another. In the brain, for example, axonal delays between brain areas can amount to several tens of milliseconds, adding an intrinsic component to any timing-based processing of information. Inferring neural interaction delays is thus needed to interpret the information transfer revealed by any analysis of directed interactions across brain structures. However, a robust estimation of interaction delays from neural activity faces several challenges if modeling assumptions on interaction mechanisms are wrong or cannot be made. Here, we propose a robust estimator for neuronal interaction delays rooted in an information-theoretic framework, which allows a model-free exploration of interactions. In particular, we extend transfer entropy to account for delayed source-target interactions, while crucially retaining the conditioning on the embedded target state at the immediately previous time step. We prove that this particular extension is indeed guaranteed to identify interaction delays between two coupled systems and is the only relevant option in keeping with Wiener's principle of causality. We demonstrate the performance of our approach in detecting interaction delays on finite data by numerical simulations of stochastic and deterministic processes, as well as on local field potential recordings. We also show the ability of the extended transfer entropy to detect the presence of multiple delays, as well as feedback loops. While evaluated on neuroscience data, we expect the estimator to be useful in other fields dealing with network dynamics. PMID:23468850

  14. Information transfer in continuous processes

    NASA Astrophysics Data System (ADS)

    Kaiser, A.; Schreiber, T.

    2002-06-01

    We discuss a recently proposed quantity, called transfer entropy, which uses time series data to measure the amount of information transferred from one process to another. In order to understand its foundation, merits, and limitations, we review some aspects of information theoretic functionals. While for symbol sequences these measures have an intuitive interpretation, their application to continuous state processes and, in particular, their estimation from finite data sets is problematic. For mutual information, finite length scale estimates converge from below and can thus be used to reject the assumption that the observed processes are independent. However, mutual information does not provide any directional information. Conversely, transfer entropy does resolve the directionality of information exchange but no similar monotonic convergence seems to hold. Thus, only in the case of zero transfer entropy in one direction we can reliably infer an asymmetry of the information exchange.

  15. Heat Transfer in Complex Fluids

    SciTech Connect

    Mehrdad Massoudi

    2012-01-01

    Amongst the most important constitutive relations in Mechanics, when characterizing the behavior of complex materials, one can identify the stress tensor T, the heat flux vector q (related to heat conduction) and the radiant heating (related to the radiation term in the energy equation). Of course, the expression 'complex materials' is not new. In fact, at least since the publication of the paper by Rivlin & Ericksen (1955), who discussed fluids of complexity (Truesdell & Noll, 1992), to the recently published books (Deshpande et al., 2010), the term complex fluids refers in general to fluid-like materials whose response, namely the stress tensor, is 'non-linear' in some fashion. This non-linearity can manifest itself in variety of forms such as memory effects, yield stress, creep or relaxation, normal-stress differences, etc. The emphasis in this chapter, while focusing on the constitutive modeling of complex fluids, is on granular materials (such as coal) and non-linear fluids (such as coal-slurries). One of the main areas of interest in energy related processes, such as power plants, atomization, alternative fuels, etc., is the use of slurries, specifically coal-water or coal-oil slurries, as the primary fuel. Some studies indicate that the viscosity of coal-water mixtures depends not only on the volume fraction of solids, and the mean size and the size distribution of the coal, but also on the shear rate, since the slurry behaves as shear-rate dependent fluid. There are also studies which indicate that preheating the fuel results in better performance, and as a result of such heating, the viscosity changes. Constitutive modeling of these non-linear fluids, commonly referred to as non-Newtonian fluids, has received much attention. Most of the naturally occurring and synthetic fluids are non-linear fluids, for example, polymer melts, suspensions, blood, coal-water slurries, drilling fluids, mud, etc. It should be noted that sometimes these fluids show Newtonian

  16. Unifying Complexity and Information

    NASA Astrophysics Data System (ADS)

    Ke, Da-Guan

    2013-04-01

    Complex systems, arising in many contexts in the computer, life, social, and physical sciences, have not shared a generally-accepted complexity measure playing a fundamental role as the Shannon entropy H in statistical mechanics. Superficially-conflicting criteria of complexity measurement, i.e. complexity-randomness (C-R) relations, have given rise to a special measure intrinsically adaptable to more than one criterion. However, deep causes of the conflict and the adaptability are not much clear. Here I trace the root of each representative or adaptable measure to its particular universal data-generating or -regenerating model (UDGM or UDRM). A representative measure for deterministic dynamical systems is found as a counterpart of the H for random process, clearly redefining the boundary of different criteria. And a specific UDRM achieving the intrinsic adaptability enables a general information measure that ultimately solves all major disputes. This work encourages a single framework coving deterministic systems, statistical mechanics and real-world living organisms.

  17. Information communication on complex networks

    NASA Astrophysics Data System (ADS)

    Igarashi, Akito; Kawamoto, Hiroki; Maruyama, Takahiro; Morioka, Atsushi; Naganuma, Yuki

    2013-02-01

    Since communication networks such as the Internet, which is regarded as a complex network, have recently become a huge scale and a lot of data pass through them, the improvement of packet routing strategies for transport is one of the most significant themes in the study of computer networks. It is especially important to find routing strategies which can bear as many traffic as possible without congestion in complex networks. First, using neural networks, we introduce a strategy for packet routing on complex networks, where path lengths and queue lengths in nodes are taken into account within a framework of statistical physics. Secondly, instead of using shortest paths, we propose efficient paths which avoid hubs, nodes with a great many degrees, on scale-free networks with a weight of each node. We improve the heuristic algorithm proposed by Danila et. al. which optimizes step by step routing properties on congestion by using the information of betweenness, the probability of paths passing through a node in all optimal paths which are defined according to a rule, and mitigates the congestion. We confirm the new heuristic algorithm which balances traffic on networks by achieving minimization of the maximum betweenness in much smaller number of iteration steps. Finally, We model virus spreading and data transfer on peer-to-peer (P2P) networks. Using mean-field approximation, we obtain an analytical formulation and emulate virus spreading on the network and compare the results with those of simulation. Moreover, we investigate the mitigation of information traffic congestion in the P2P networks.

  18. Promoting Transfer by Grounding Complex Systems Principles

    ERIC Educational Resources Information Center

    Goldstone, Robert L.; Wilensky, Uri

    2008-01-01

    Understanding scientific phenomena in terms of complex systems principles is both scientifically and pedagogically important. Situations from different disciplines of science are often governed by the same principle, and so promoting knowledge transfer across disciplines makes valuable cross-fertilization and scientific unification possible.…

  19. Information Flows? A Critique of Transfer Entropies

    NASA Astrophysics Data System (ADS)

    James, Ryan G.; Barnett, Nix; Crutchfield, James P.

    2016-06-01

    A central task in analyzing complex dynamics is to determine the loci of information storage and the communication topology of information flows within a system. Over the last decade and a half, diagnostics for the latter have come to be dominated by the transfer entropy. Via straightforward examples, we show that it and a derivative quantity, the causation entropy, do not, in fact, quantify the flow of information. At one and the same time they can overestimate flow or underestimate influence. We isolate why this is the case and propose several avenues to alternate measures for information flow. We also address an auxiliary consequence: The proliferation of networks as a now-common theoretical model for large-scale systems, in concert with the use of transferlike entropies, has shoehorned dyadic relationships into our structural interpretation of the organization and behavior of complex systems. This interpretation thus fails to include the effects of polyadic dependencies. The net result is that much of the sophisticated organization of complex systems may go undetected.

  20. Information Flows? A Critique of Transfer Entropies.

    PubMed

    James, Ryan G; Barnett, Nix; Crutchfield, James P

    2016-06-10

    A central task in analyzing complex dynamics is to determine the loci of information storage and the communication topology of information flows within a system. Over the last decade and a half, diagnostics for the latter have come to be dominated by the transfer entropy. Via straightforward examples, we show that it and a derivative quantity, the causation entropy, do not, in fact, quantify the flow of information. At one and the same time they can overestimate flow or underestimate influence. We isolate why this is the case and propose several avenues to alternate measures for information flow. We also address an auxiliary consequence: The proliferation of networks as a now-common theoretical model for large-scale systems, in concert with the use of transferlike entropies, has shoehorned dyadic relationships into our structural interpretation of the organization and behavior of complex systems. This interpretation thus fails to include the effects of polyadic dependencies. The net result is that much of the sophisticated organization of complex systems may go undetected. PMID:27341264

  1. Coronene-based charge-transfer complexes

    NASA Astrophysics Data System (ADS)

    Yoshida, Yukihiro; Isomura, Kazuhide; Kumagai, Yoshihide; Maesato, Mitsuhiko; Kishida, Hideo; Mizuno, Motohiro; Saito, Gunzi

    2016-08-01

    Recent developments in the arena of charge-transfer complexes composed of the D 6h-symmetric polycyclic aromatic hydrocarbon, coronene, are highlighted with emphasis on the structural and physical properties of these complexes. Because of the dual electron-donating and -accepting abilities of coronene, this group involves structurally-defined four cation salts and three anion salts. The Jahn–Teller distortions and in-plane motion of coronene molecules in the solids, both of which are closely associated with the high symmetry of coronene molecules, and syntheses of clathrate-type complexes are also presented.

  2. Coronene-based charge-transfer complexes.

    PubMed

    Yoshida, Yukihiro; Isomura, Kazuhide; Kumagai, Yoshihide; Maesato, Mitsuhiko; Kishida, Hideo; Mizuno, Motohiro; Saito, Gunzi

    2016-08-01

    Recent developments in the arena of charge-transfer complexes composed of the D 6h-symmetric polycyclic aromatic hydrocarbon, coronene, are highlighted with emphasis on the structural and physical properties of these complexes. Because of the dual electron-donating and -accepting abilities of coronene, this group involves structurally-defined four cation salts and three anion salts. The Jahn-Teller distortions and in-plane motion of coronene molecules in the solids, both of which are closely associated with the high symmetry of coronene molecules, and syntheses of clathrate-type complexes are also presented. PMID:27294380

  3. Plasmodesmata: gateways for information transfer.

    PubMed

    Waigmann, E; Cohen, Y; McLean, G; Zambryski, P

    1998-01-01

    Intercellular communication in plants has evolved to occur via elongated cytoplasmic bridges, called plasmodesmata, that traverse the thick cell walls that surround plant cells. Historically, plasmodesmata have been assigned the mostly passive role of creating cytoplasmic continuity between plant cells enabling free transport of the wealth of small plant metabolites and growth hormones under 1 kDa. When it was discovered that plant viruses pirate plasmodesmata for movement of viral genomes during infection, it was proposed that viruses modified plasmodesmata for transport of very large molecules. Now, there is compelling evidence that plasmodesmata are inherently dynamic, rapidly altering their dimensions to increase their transport capabilities, upon contact with viral as well as developmentally important plant proteins. Further, the study of intercellular transport has prompted analyses of intracellular transport pathways, implicating the cytoskeleton as a major tracking system to plasmodesmata. Thus, plasmodesmata form a three-dimensional network of transportation channels and major checkpoints for information transfer. In the following, current knowledge about structure and function of these connective organelles, and about routing of molecules towards plasmodesmata, will be summarized. PMID:10645422

  4. Information Complexity and Biology

    NASA Astrophysics Data System (ADS)

    Bagnoli, Franco; Bignone, Franco A.; Cecconi, Fabio; Politi, Antonio

    Kolmogorov contributed directly to Biology in essentially three problems: the analysis of population dynamics (Lotka-Volterra equations), the reaction-diffusion formulation of gene spreading (FKPP equation), and some discussions about Mendel's laws. However, the widely recognized importance of his contribution arises from his work on algorithmic complexity. In fact, the limited direct intervention in Biology reflects the generally slow growth of interest of mathematicians towards biological issues. From the early work of Vito Volterra on species competition, to the slow growth of dynamical systems theory, contributions to the study of matter and the physiology of the nervous system, the first 50-60 years have witnessed important contributions, but as scattered pieces apparently uncorrelated, and in branches often far away from Biology. Up to the 40' it is hard to see the initial loose build up of a convergence, for those theories that will become mainstream research by the end of the century, and connected by the study of biological systems per-se.

  5. Dynamic information routing in complex networks

    PubMed Central

    Kirst, Christoph; Timme, Marc; Battaglia, Demian

    2016-01-01

    Flexible information routing fundamentally underlies the function of many biological and artificial networks. Yet, how such systems may specifically communicate and dynamically route information is not well understood. Here we identify a generic mechanism to route information on top of collective dynamical reference states in complex networks. Switching between collective dynamics induces flexible reorganization of information sharing and routing patterns, as quantified by delayed mutual information and transfer entropy measures between activities of a network's units. We demonstrate the power of this mechanism specifically for oscillatory dynamics and analyse how individual unit properties, the network topology and external inputs co-act to systematically organize information routing. For multi-scale, modular architectures, we resolve routing patterns at all levels. Interestingly, local interventions within one sub-network may remotely determine nonlocal network-wide communication. These results help understanding and designing information routing patterns across systems where collective dynamics co-occurs with a communication function. PMID:27067257

  6. Dynamic information routing in complex networks.

    PubMed

    Kirst, Christoph; Timme, Marc; Battaglia, Demian

    2016-01-01

    Flexible information routing fundamentally underlies the function of many biological and artificial networks. Yet, how such systems may specifically communicate and dynamically route information is not well understood. Here we identify a generic mechanism to route information on top of collective dynamical reference states in complex networks. Switching between collective dynamics induces flexible reorganization of information sharing and routing patterns, as quantified by delayed mutual information and transfer entropy measures between activities of a network's units. We demonstrate the power of this mechanism specifically for oscillatory dynamics and analyse how individual unit properties, the network topology and external inputs co-act to systematically organize information routing. For multi-scale, modular architectures, we resolve routing patterns at all levels. Interestingly, local interventions within one sub-network may remotely determine nonlocal network-wide communication. These results help understanding and designing information routing patterns across systems where collective dynamics co-occurs with a communication function. PMID:27067257

  7. Dynamic information routing in complex networks

    NASA Astrophysics Data System (ADS)

    Kirst, Christoph; Timme, Marc; Battaglia, Demian

    2016-04-01

    Flexible information routing fundamentally underlies the function of many biological and artificial networks. Yet, how such systems may specifically communicate and dynamically route information is not well understood. Here we identify a generic mechanism to route information on top of collective dynamical reference states in complex networks. Switching between collective dynamics induces flexible reorganization of information sharing and routing patterns, as quantified by delayed mutual information and transfer entropy measures between activities of a network's units. We demonstrate the power of this mechanism specifically for oscillatory dynamics and analyse how individual unit properties, the network topology and external inputs co-act to systematically organize information routing. For multi-scale, modular architectures, we resolve routing patterns at all levels. Interestingly, local interventions within one sub-network may remotely determine nonlocal network-wide communication. These results help understanding and designing information routing patterns across systems where collective dynamics co-occurs with a communication function.

  8. Stratospheric Aerosols: The Transfer of Scientific Information.

    ERIC Educational Resources Information Center

    Feidler, Anita; Hurt, C. D.

    1986-01-01

    Examines information transfer in atmospheric physics by tracing one paper through five years of citations and suggesting patterns for highly cited papers. The results are also discussed in terms of information transfer in a popularized environment, as stratospheric aerosols have been prominently discussed in the popular press. (Author/EM)

  9. Darwinian demons, evolutionary complexity, and information maximization.

    PubMed

    Krakauer, David C

    2011-09-01

    Natural selection is shown to be an extended instance of a Maxwell's demon device. A demonic selection principle is introduced that states that organisms cannot exceed the complexity of their selective environment. Thermodynamic constraints on error repair impose a fundamental limit to the rate that information can be transferred from the environment (via the selective demon) to the genome. Evolved mechanisms of learning and inference can overcome this limitation, but remain subject to the same fundamental constraint, such that plastic behaviors cannot exceed the complexity of reward signals. A natural measure of evolutionary complexity is provided by mutual information, and niche construction activity--the organismal contribution to the construction of selection pressures--might in principle lead to its increase, bounded by thermodynamic free energy required for error correction. PMID:21974673

  10. Accessing complexity from genome information

    NASA Astrophysics Data System (ADS)

    Tenreiro Machado, J. A.

    2012-06-01

    This paper studies the information content of the chromosomes of 24 species. In a first phase, a scheme inspired in dynamical system state space representation is developed. For each chromosome the state space dynamical evolution is shed into a two dimensional chart. The plots are then analyzed and characterized in the perspective of fractal dimension. This information is integrated in two measures of the species' complexity addressing its average and variability. The results are in close accordance with phylogenetics pointing quantitative aspects of the species' genomic complexity.

  11. Information transfer in the National Airspace System

    NASA Technical Reports Server (NTRS)

    Lee, Alfred T.

    1988-01-01

    An informal overview is given of the work in progress and the planned work in the area of information transfer that specifically addresses human factors issues in National Airspace System (NAS). The issues of how weather information will be displayed on the flight deck, the development of appropriate decision making technology, and digital datalink transmission are also briefly discussed.

  12. Embedded information transfer technology assessment

    NASA Astrophysics Data System (ADS)

    Huff, L. A.; Moreland, J.; Allison, R.; Elia, J.; Jerdee, B.

    1984-04-01

    The objective of this study is to develop approaches for improved Line Replaceable Unit (LRU) internal communications, utilizing state-of-the-art techniques and technology, in order to reduce the growing number of interconnects with LRU's. Worst-case LRU data transfer requirements were established by analyzing internal signal routing, data rates, and duty cycles of the F-16 Fire Control Computer (FCC) and the Programmable Signal Processor (PSP). It was determined that 25/Mword/second is adequate for card-to-backplane (serial) transfers. Candidate designs for meeting these requirements were developed and then subjected to an extensive trade-off analysis. This analysis ultimately yielded the selection of Switched Network Electro-Optical (serial) and Electro-Optical Air-Gap (parallel) as the preferred approaches. The interface pin-count per module of the recommended designs has been reduced to approximately 40. This is substantially lower that the average of 250 connections per module in most conventional approaches and fulfills the primary objective of this program. Further, the zero insertion-force air-gap interfaces directly support modular architectures and enhance the prospects of making two-level maintenance concepts a practical reality.

  13. Entropy, complexity, and spatial information

    NASA Astrophysics Data System (ADS)

    Batty, Michael; Morphet, Robin; Masucci, Paolo; Stanilov, Kiril

    2014-10-01

    We pose the central problem of defining a measure of complexity, specifically for spatial systems in general, city systems in particular. The measures we adopt are based on Shannon's (in Bell Syst Tech J 27:379-423, 623-656, 1948) definition of information. We introduce this measure and argue that increasing information is equivalent to increasing complexity, and we show that for spatial distributions, this involves a trade-off between the density of the distribution and the number of events that characterize it; as cities get bigger and are characterized by more events—more places or locations, information increases, all other things being equal. But sometimes the distribution changes at a faster rate than the number of events and thus information can decrease even if a city grows. We develop these ideas using various information measures. We first demonstrate their applicability to various distributions of population in London over the last 100 years, then to a wider region of London which is divided into bands of zones at increasing distances from the core, and finally to the evolution of the street system that characterizes the built-up area of London from 1786 to the present day. We conclude by arguing that we need to relate these measures to other measures of complexity, to choose a wider array of examples, and to extend the analysis to two-dimensional spatial systems.

  14. Entropy, complexity, and spatial information

    NASA Astrophysics Data System (ADS)

    Batty, Michael; Morphet, Robin; Masucci, Paolo; Stanilov, Kiril

    2014-09-01

    We pose the central problem of defining a measure of complexity, specifically for spatial systems in general, city systems in particular. The measures we adopt are based on Shannon's (in Bell Syst Tech J 27:379-423, 623-656, 1948) definition of information. We introduce this measure and argue that increasing information is equivalent to increasing complexity, and we show that for spatial distributions, this involves a trade-off between the density of the distribution and the number of events that characterize it; as cities get bigger and are characterized by more events—more places or locations, information increases, all other things being equal. But sometimes the distribution changes at a faster rate than the number of events and thus information can decrease even if a city grows. We develop these ideas using various information measures. We first demonstrate their applicability to various distributions of population in London over the last 100 years, then to a wider region of London which is divided into bands of zones at increasing distances from the core, and finally to the evolution of the street system that characterizes the built-up area of London from 1786 to the present day. We conclude by arguing that we need to relate these measures to other measures of complexity, to choose a wider array of examples, and to extend the analysis to two-dimensional spatial systems.

  15. Quantifying ‘Causality’ in Complex Systems: Understanding Transfer Entropy

    PubMed Central

    Abdul Razak, Fatimah; Jensen, Henrik Jeldtoft

    2014-01-01

    ‘Causal’ direction is of great importance when dealing with complex systems. Often big volumes of data in the form of time series are available and it is important to develop methods that can inform about possible causal connections between the different observables. Here we investigate the ability of the Transfer Entropy measure to identify causal relations embedded in emergent coherent correlations. We do this by firstly applying Transfer Entropy to an amended Ising model. In addition we use a simple Random Transition model to test the reliability of Transfer Entropy as a measure of ‘causal’ direction in the presence of stochastic fluctuations. In particular we systematically study the effect of the finite size of data sets. PMID:24955766

  16. Information transfer for small-amplitude signals

    NASA Astrophysics Data System (ADS)

    Kostal, Lubomir; Lansky, Petr

    2010-05-01

    We study the optimality conditions of information transfer in systems with memory in the low signal-to-noise ratio regime of vanishing input amplitude. We find that the optimal mutual information is represented by a maximum variance of the signal time course, with correlation structure determined by the Fisher information matrix. We provide illustration of the method on a simple biologically inspired model of electrosensory neuron. Our general results apply also to the study of information transfer in single neurons subject to weak stimulation, with implications to the problem of coding efficiency in biological systems.

  17. Information transfer in community structured multiplex networks

    NASA Astrophysics Data System (ADS)

    Solé Ribalta, Albert; Granell, Clara; Gómez, Sergio; Arenas, Alex

    2015-08-01

    The study of complex networks that account for different types of interactions has become a subject of interest in the last few years, specially because its representational power in the description of users interactions in diverse online social platforms (Facebook, Twitter, Instagram, etc.). The mathematical description of these interacting networks has been coined under the name of multilayer networks, where each layer accounts for a type of interaction. It has been shown that diffusive processes on top of these networks present a phenomenology that cannot be explained by the naive superposition of single layer diffusive phenomena but require the whole structure of interconnected layers. Nevertheless, the description of diffusive phenomena on multilayer networks has obviated the fact that social networks have strong mesoscopic structure represented by different communities of individuals driven by common interests, or any other social aspect. In this work, we study the transfer of information in multilayer networks with community structure. The final goal is to understand and quantify, if the existence of well-defined community structure at the level of individual layers, together with the multilayer structure of the whole network, enhances or deteriorates the diffusion of packets of information.

  18. The information transfer problem summary and comments

    NASA Technical Reports Server (NTRS)

    Billings, C. E.; Cheaney, E. S.

    1981-01-01

    An attempt is made to illuminate the problems associated with deficiencies in the information transfer process of both intracockpit and air/ground communications. Possible steps are suggested as a means of enhancing the flow of information in the aviation system.

  19. Information Dissemination and Technology Transfer in Telecommunications.

    ERIC Educational Resources Information Center

    Roderer, Nancy K.; King, Donald W.

    Using a model of scientific and technical information transfer as a framework, this document focuses on four types of activities: the generation or authorship of telecommunications information and its publication, distribution, and use. Different forms of publication are considered in each functional area, though primary emphasis is on the…

  20. Information Technology in Complex Health Services

    PubMed Central

    Southon, Frank Charles Gray; Sauer, Chris; Dampney, Christopher Noel Grant (Kit)

    1997-01-01

    Abstract Objective: To identify impediments to the successful transfer and implementation of packaged information systems through large, divisionalized health services. Design: A case analysis of the failure of an implementation of a critical application in the Public Health System of the State of New South Wales, Australia, was carried out. This application had been proven in the United States environment. Measurements: Interviews involving over 60 staff at all levels of the service were undertaken by a team of three. The interviews were recorded and analyzed for key themes, and the results were shared and compared to enable a continuing critical assessment. Results: Two components of the transfer of the system were considered: the transfer from a different environment, and the diffusion throughout a large, divisionalized organization. The analyses were based on the Scott-Morton organizational fit framework. In relation to the first, it was found that there was a lack of fit in the business environments and strategies, organizational structures and strategy-structure pairing as well as the management process-roles pairing. The diffusion process experienced problems because of the lack of fit in the strategy-structure, strategy-structure-management processes, and strategy-structure-role relationships. Conclusion: The large-scale developments of integrated health services present great challenges to the efficient and reliable implementation of information technology, especially in large, divisionalized organizations. There is a need to take a more sophisticated approach to understanding the complexities of organizational factors than has traditionally been the case. PMID:9067877

  1. Single Molecule Electron Transfer Process of Ruthenium Complexes.

    SciTech Connect

    Hu, Dehong; Lu, H PETER.

    2006-03-01

    Transition metal complexes such as ruthenium complexes, having metal-to-ligand charge transfer states, are extensively used in solar energy conversion and electron transfer in biological systems and at interfaces. The dynamics of metal-to-ligand charge transfer and subsequent intermolecular, intramolecular, and interfacial electron transfer processes can be highly complex and inhomogeneous, especially when molecules are involved in interactions and perturbations from heterogeneous local environments and gated by conformation fluctuations. We have employed the single-molecule spectroscopy, a powerful approach for inhomogeneous systems to study the electron transfer dynamics of ruthenium complexes. We have applied a range of statistical analysis methods to reveal nonclassical photon emission behavior of the single ruthenium complex, i.e., photon antibunching, and photophysical ground-state recovering dynamics on a microsecond time scale. The use of photon antibunching to measure phosphorescence lifetimes and single-molecule electron transfer dynamics at room temperature is demonstrated.

  2. Information Horizons in Complex Networks

    NASA Astrophysics Data System (ADS)

    Sneppen, Kim

    2005-03-01

    We investigate how the structure constrain specific communication in social-, man-made and biological networks. We find that human networks of governance and collaboration are predictable on teat-a-teat level, reflecting well defined pathways, but globally inefficient (1). In contrast, the Internet tends to have better overall communication abilities, more alternative pathways, and is therefore more robust. Between these extremes are the molecular network of living organisms. Further, for most real world networks we find that communication ability is favored by topology on small distances, but disfavored at larger distances (2,3,4). We discuss the topological implications in terms of modularity and the positioning of hubs in the networks (5,6). Finally we introduce some simple models which demonstarte how communication may shape the structure of in particular man made networks (7,8). 1) K. Sneppen, A. Trusina, M. Rosvall (2004). Hide and seek on complex networks [cond-mat/0407055] 2) M. Rosvall, A. Trusina, P. Minnhagen and K. Sneppen (2004). Networks and Cities: An Information Perspective [cond-mat/0407054]. In PRL. 3) A. Trusina, M. Rosvall, K. Sneppen (2004). Information Horizons in Networks. [cond-mat/0412064] 4) M. Rosvall, P. Minnhagen, K. Sneppen (2004). Navigating Networks with Limited Information. [cond-mat/0412051] 5) S. Maslov and K. Sneppen (2002). Specificity and stability in topology of protein networks Science 296, 910-913 [cond-mat/0205380]. 6) A. Trusina, S. Maslov, P. Minnhagen, K. Sneppen Hierarchy Measures in Complex Networks. Phys. Rev. Lett. 92, 178702 [cond-mat/0308339]. 7) M. Rosvall and K. Sneppen (2003). Modeling Dynamics of Information Networks. Phys. Rev. Lett. 91, 178701 [cond-mat/0308399]. 8) B-J. Kim, A. Trusina, P. Minnhagen, K. Sneppen (2003). Self Organized Scale-Free Networks from Merging and Regeneration. nlin.AO/0403006. In European Journal of Physics.

  3. Quantum information and entanglement transfer for qutrits

    NASA Astrophysics Data System (ADS)

    Delgado, A.; Saavedra, C.; Retamal, J. C.

    2007-10-01

    We propose a scheme for the transfer of quantum information among distant qutrits. We apply this scheme to the distribution of entanglement of qutrits states among distant nodes and to the generation of multipartite antisymmetric states. We also discuss applications to quantum secret sharing.

  4. Noise enhances information transfer in hierarchical networks.

    PubMed

    Czaplicka, Agnieszka; Holyst, Janusz A; Sloot, Peter M A

    2013-01-01

    We study the influence of noise on information transmission in the form of packages shipped between nodes of hierarchical networks. Numerical simulations are performed for artificial tree networks, scale-free Ravasz-Barabási networks as well for a real network formed by email addresses of former Enron employees. Two types of noise are considered. One is related to packet dynamics and is responsible for a random part of packets paths. The second one originates from random changes in initial network topology. We find that the information transfer can be enhanced by the noise. The system possesses optimal performance when both kinds of noise are tuned to specific values, this corresponds to the Stochastic Resonance phenomenon. There is a non-trivial synergy present for both noisy components. We found also that hierarchical networks built of nodes of various degrees are more efficient in information transfer than trees with a fixed branching factor. PMID:23390574

  5. Noise enhances information transfer in hierarchical networks

    PubMed Central

    Czaplicka, Agnieszka; Holyst, Janusz A.; Sloot, Peter M. A.

    2013-01-01

    We study the influence of noise on information transmission in the form of packages shipped between nodes of hierarchical networks. Numerical simulations are performed for artificial tree networks, scale-free Ravasz-Barabási networks as well for a real network formed by email addresses of former Enron employees. Two types of noise are considered. One is related to packet dynamics and is responsible for a random part of packets paths. The second one originates from random changes in initial network topology. We find that the information transfer can be enhanced by the noise. The system possesses optimal performance when both kinds of noise are tuned to specific values, this corresponds to the Stochastic Resonance phenomenon. There is a non-trivial synergy present for both noisy components. We found also that hierarchical networks built of nodes of various degrees are more efficient in information transfer than trees with a fixed branching factor. PMID:23390574

  6. Genetic information transfer promotes cooperation in bacteria.

    PubMed

    Dimitriu, Tatiana; Lotton, Chantal; Bénard-Capelle, Julien; Misevic, Dusan; Brown, Sam P; Lindner, Ariel B; Taddei, François

    2014-07-29

    Many bacterial species are social, producing costly secreted "public good" molecules that enhance the growth of neighboring cells. The genes coding for these cooperative traits are often propagated via mobile genetic elements and can be virulence factors from a biomedical perspective. Here, we present an experimental framework that links genetic information exchange and the selection of cooperative traits. Using simulations and experiments based on a synthetic bacterial system to control public good secretion and plasmid conjugation, we demonstrate that horizontal gene transfer can favor cooperation. In a well-mixed environment, horizontal transfer brings a direct infectious advantage to any gene, regardless of its cooperation properties. However, in a structured population transfer selects specifically for cooperation by increasing the assortment among cooperative alleles. Conjugation allows cooperative alleles to overcome rarity thresholds and invade bacterial populations structured purely by stochastic dilution effects. Our results provide an explanation for the prevalence of cooperative genes on mobile elements, and suggest a previously unidentified benefit of horizontal gene transfer for bacteria. PMID:25024219

  7. Genetic information transfer promotes cooperation in bacteria

    PubMed Central

    Dimitriu, Tatiana; Lotton, Chantal; Bénard-Capelle, Julien; Misevic, Dusan; Brown, Sam P.; Lindner, Ariel B.; Taddei, François

    2014-01-01

    Many bacterial species are social, producing costly secreted “public good” molecules that enhance the growth of neighboring cells. The genes coding for these cooperative traits are often propagated via mobile genetic elements and can be virulence factors from a biomedical perspective. Here, we present an experimental framework that links genetic information exchange and the selection of cooperative traits. Using simulations and experiments based on a synthetic bacterial system to control public good secretion and plasmid conjugation, we demonstrate that horizontal gene transfer can favor cooperation. In a well-mixed environment, horizontal transfer brings a direct infectious advantage to any gene, regardless of its cooperation properties. However, in a structured population transfer selects specifically for cooperation by increasing the assortment among cooperative alleles. Conjugation allows cooperative alleles to overcome rarity thresholds and invade bacterial populations structured purely by stochastic dilution effects. Our results provide an explanation for the prevalence of cooperative genes on mobile elements, and suggest a previously unidentified benefit of horizontal gene transfer for bacteria. PMID:25024219

  8. Information highway and numerical heat transfer

    SciTech Connect

    Shih, T.M.; Minkowycz, W.J.

    1996-11-22

    It is proposed that researchers in the numerical heat transfer community need to realize the trend of the information highway and agree to use a protocol or a module that constitutes the core of a computer program solving heat transfer problems. This will avoid duplicate programming and accelerate the technology advancement of numerical heat transfer. The module for two-dimensional incompressible Navier-Stokes flows is presented and explained. It is further demonstrated that, using this module as the foundation, the user can straightforwardly build up an entire personal computer code by inputting the data, specifying boundary conditions, and outputting the result. Other modules for slightly more complicated problems, such as transient flows with variable viscosity in irregular geometries, are also presented. Other than zoning matches for problems with multizones, the programming task for a user becomes minimal and simple: input, prescribe the boundary conditions, and output. The availability of Navier-Stokes modules is particularly helpful for less experienced numerical researchers, newcomers, and graduate students who have just entered the area of heat transfer and fluid flows.

  9. Anesthesia-related changes in information transfer may be caused by reduction in local information generation.

    PubMed

    Wollstadt, Patricia; Sellers, Kristin K; Hutt, Axel; Frohlich, Flavio; Wibral, Michael

    2015-08-01

    In anesthesia research it is an open question how general anesthetics lead to loss of consciousness (LOC). It has been proposed that LOC may be caused by the disruption of cortical information processing, preventing information integration. Therefore, recent studies investigating information processing under anesthesia focused on changes in information transfer, measured by transfer entropy (TE). However, often this complex technique was not applied rigorously, using time series in symbolic representation, or using TE differences without accounting for neural conduction delays, or without accounting for signal history. Here, we used current best-practice in TE estimation to investigate information transfer under anesthesia: We conducted simultaneous recordings in primary visual cortex (V1) and prefrontal cortex (PFC) of head-fixed ferrets in a dark environment under different levels of anesthesia (awake, 0.5% isoflurane, 1.0 % isoflurane). To elucidate reasons for changes in TE, we further quantified information processing within brain areas by estimating active information storage (AIS) as an estimator of predictable information, and Lempel-Ziv complexity (LZC) as an estimator of signal entropy. Under anesthesia, we found a reduction in information transfer (TE) between PFC and V1 with a stronger reduction for the feedback direction (PFC to V1), validating previous results. Furthermore, entropy (LZC) was reduced and activity became more predictable as indicated by higher values of AIS. We conclude that higher anesthesia concentrations indeed lead to reduced inter-areal information transfer, which may be partly caused by decreases in local entropy and increases in local predictability. In revealing a possible reason for reduced TE that is potentially independent of inter-areal coupling, we demonstrate the value of directly quantifying information processing in addition to focusing on dynamic properties such as coupling strength. PMID:26737182

  10. Toward the quality evaluation of complex information systems

    NASA Astrophysics Data System (ADS)

    Todoran, Ion-George; Lecornu, Laurent; Khenchaf, Ali; Le Caillec, Jean-Marc

    2014-06-01

    Recent technological evolutions and developments allow gathering huge amounts of data stemmed from different types of sensors, social networks, intelligence reports, distributed databases, etc. Data quantity and heterogeneity imposed the evolution necessity of the information systems. Nowadays the information systems are based on complex information processing techniques at multiple processing stages. Unfortunately, possessing large quantities of data and being able to implement complex algorithms do not guarantee that the extracted information will be of good quality. The decision-makers need good quality information in the process of decision-making. We insist that for a decision-maker the information and the information quality, viewed as a meta-information, are of great importance. A system not proposing to its user the information quality is in danger of not being correctly used or in more dramatic cases not to be used at all. In literature, especially in organizations management and in information retrieval, can be found some information quality evaluation methodologies. But none of these do not allow the information quality evaluation in complex and changing environments. We propose a new information quality methodology capable of estimating the information quality dynamically with data changes and/or with the information system inner changes. Our methodology is able to instantaneously update the system's output quality. For capturing the information quality changes through the system, we introduce the notion of quality transfer function. It is equivalent to the signal processing transfer function but working on the quality level. The quality transfer function describes the influence of a processing module over the information quality. We also present two different views over the notion of information quality: a global one, characterizing the entire system and a local one, for each processing module.

  11. Information transfer network of global market indices

    NASA Astrophysics Data System (ADS)

    Kim, Yup; Kim, Jinho; Yook, Soon-Hyung

    2015-07-01

    We study the topological properties of the information transfer networks (ITN) of the global financial market indices for six different periods. ITN is a directed weighted network, in which the direction and weight are determined by the transfer entropy between market indices. By applying the threshold method, it is found that ITN undergoes a crossover from the complete graph to a small-world (SW) network. SW regime of ITN for a global crisis is found to be much more enhanced than that for ordinary periods. Furthermore, when ITN is in SW regime, the average clustering coefficient is found to be synchronized with average volatility of markets. We also compare the results with the topological properties of correlation networks.

  12. Cyclopentadiene-mediated hydride transfer from rhodium complexes.

    PubMed

    Pitman, C L; Finster, O N L; Miller, A J M

    2016-07-12

    Attempts to generate a proposed rhodium hydride catalytic intermediate instead resulted in isolation of (Cp*H)Rh(bpy)Cl (1), a pentamethylcyclopentadiene complex, formed by C-H bond-forming reductive elimination from the fleeting rhodium hydride. The hydride transfer ability of diene 1 was explored through thermochemistry and hydride transfer reactions, including the reduction of NAD(+). PMID:26949917

  13. Size-Independent Energy Transfer in Biomimetic Nanoring Complexes.

    PubMed

    Parkinson, Patrick; Kamonsutthipaijit, Nuntaporn; Anderson, Harry L; Herz, Laura M

    2016-06-28

    Supramolecular antenna-ring complexes are of great interest due to their presence in natural light-harvesting complexes. While such systems are known to provide benefits through robust and efficient energy funneling, the relationship between molecular structure, strain (governed by nuclear coordinates and motion), and energy dynamics (arising from electronic behavior) is highly complex. We present a synthetic antenna-nanoring system based on a series of conjugated porphyrin chromophores ideally suited to explore such effects. By systematically varying the size of the acceptor nanoring, we reveal the interplay between antenna-nanoring binding, local strain, and energy dynamics on the picosecond time scale. Binding of the antenna unit creates a local strain in the nanoring, and this strain was measured as a function of the size of the nanoring, by UV-vis-NIR titration, providing information on the conformational flexibility of the system. Strikingly, the energy-transfer rate is independent of nanoring size, indicating the existence of strain-localized acceptor states, spread over about six porphyrin units, arising from the noncovalent antenna-nanoring association. PMID:27176553

  14. Size-Independent Energy Transfer in Biomimetic Nanoring Complexes

    PubMed Central

    2016-01-01

    Supramolecular antenna-ring complexes are of great interest due to their presence in natural light-harvesting complexes. While such systems are known to provide benefits through robust and efficient energy funneling, the relationship between molecular structure, strain (governed by nuclear coordinates and motion), and energy dynamics (arising from electronic behavior) is highly complex. We present a synthetic antenna-nanoring system based on a series of conjugated porphyrin chromophores ideally suited to explore such effects. By systematically varying the size of the acceptor nanoring, we reveal the interplay between antenna-nanoring binding, local strain, and energy dynamics on the picosecond time scale. Binding of the antenna unit creates a local strain in the nanoring, and this strain was measured as a function of the size of the nanoring, by UV–vis-NIR titration, providing information on the conformational flexibility of the system. Strikingly, the energy-transfer rate is independent of nanoring size, indicating the existence of strain-localized acceptor states, spread over about six porphyrin units, arising from the noncovalent antenna-nanoring association. PMID:27176553

  15. Rich club neurons dominate Information Transfer in local cortical networks

    NASA Astrophysics Data System (ADS)

    Nigam, Sunny; Shimono, Masanori; Sporns, Olaf; Beggs, John

    2015-03-01

    The performance of complex networks depends on how they route their traffic. It is unknown how information is transferred in local cortical networks of hundreds of closely-spaced neurons. To address this, it is necessary to record simultaneously from hundreds of neurons at a spacing that matches typical axonal connection distances, and at a temporal resolution that matches synaptic delays. We used a 512 electrode array (60 μm spacing) to record spontaneous activity at 20 kHz, simultaneously from up to 700 neurons in slice cultures of mouse somatosensory cortex for 1 hr at a time. We used transfer entropy to quantify directed information transfer (IT) between pairs of neurons. We found an approximately lognormal distribution of firing rates as reported in in-vivo. Pairwise information transfer strengths also were nearly lognormally distributed, similar to synaptic strengths. 20% of the neurons accounted for 70% of the total IT coming into, and going out of the network and were defined as rich nodes. These rich nodes were more densely and strongly connected to each other expected by chance, forming a rich club. This highly uneven distribution of IT has implications for the efficiency and robustness of local cortical networks, and gives clues to the plastic processes that shape them. JSPS.

  16. Tsallis information dimension of complex networks

    NASA Astrophysics Data System (ADS)

    Zhang, Qi; Luo, Chuanhai; Li, Meizhu; Deng, Yong; Mahadevan, Sankaran

    2015-02-01

    The fractal and self-similarity properties are revealed in many complex networks. The information dimension is a useful method to describe the fractal and self-similarity properties of the complex networks. In order to show the influence of different parts in the complex networks to the information dimension, we have proposed a new information dimension based on the Tsallis entropy namely the Tsallis information dimension. The proposed information dimension is changed according to the scale which is described by the nonextensivity parameter q, and it is inverse with the nonextensivity parameter q. The existing information dimension is a special case of the Tsallis information dimension when q = 1. The Tsallis information dimension is a generalized information dimension of the complex networks.

  17. Information transfer - a look into the future

    SciTech Connect

    Fournier, M.

    1986-12-01

    This keynote address attempts to relate the interests of CODATA members in facilitating the worldwide exchange of scientific information with revolutionary new developments foreseen in the domain of telecommunications. Today's trends in telecommunications are projected into the future through two successive generations of technological evolution. The first generation of evolution starts in the relatively near future with initial implementation of functional capabilities for Integrated Service Digital Networks (ISDNs). The second generation mates the broadband transmission capability of fiber-optic cables with new concepts of fast-packet switching to afford unprecedented service flexibility. Standards development as a planning prerequisite of the future telecommunication network is discussed. Some aspects of standards development and other preliminary planning activity are suggested where possible CODATA involvement might prove advantageous in preparing to realize future objectives for information transfer.

  18. 28 CFR 22.24 - Information transfer agreement.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... STATISTICAL INFORMATION § 22.24 Information transfer agreement. Prior to the transfer of any identifiable... identifiable to a private person will be used only for research and statistical purposes. (b) Information...-know basis for research or statistical purposes, provided that such transfer is approved by the...

  19. 28 CFR 22.24 - Information transfer agreement.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... STATISTICAL INFORMATION § 22.24 Information transfer agreement. Prior to the transfer of any identifiable... identifiable to a private person will be used only for research and statistical purposes. (b) Information...-know basis for research or statistical purposes, provided that such transfer is approved by the...

  20. 28 CFR 22.24 - Information transfer agreement.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... STATISTICAL INFORMATION § 22.24 Information transfer agreement. Prior to the transfer of any identifiable... identifiable to a private person will be used only for research and statistical purposes. (b) Information...-know basis for research or statistical purposes, provided that such transfer is approved by the...

  1. 28 CFR 22.24 - Information transfer agreement.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... STATISTICAL INFORMATION § 22.24 Information transfer agreement. Prior to the transfer of any identifiable... identifiable to a private person will be used only for research and statistical purposes. (b) Information...-know basis for research or statistical purposes, provided that such transfer is approved by the...

  2. 28 CFR 22.24 - Information transfer agreement.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... STATISTICAL INFORMATION § 22.24 Information transfer agreement. Prior to the transfer of any identifiable... identifiable to a private person will be used only for research and statistical purposes. (b) Information...-know basis for research or statistical purposes, provided that such transfer is approved by the...

  3. Charge-transfer complexation between naphthalene diimides and aromatic solvents.

    PubMed

    Kulkarni, Chidambar; Periyasamy, Ganga; Balasubramanian, S; George, Subi J

    2014-07-28

    Naphthalene diimides (NDIs) form emissive ground-state charge-transfer (CT) complexes with various electron rich aromatic solvents like benzene, o-xylene and mesitylene. TD-DFT calculation of the complexes suggests CT interaction and accounts for the observed ground-state changes. PMID:24931833

  4. Primary cells utilize halogen-organic charge transfer complex

    NASA Technical Reports Server (NTRS)

    Gutmann, F.; Hermann, A. M.; Rembaum, A.

    1966-01-01

    Electrochemical cells with solid state components employ charge transfer complexes or donor-acceptor complexes in which the donor component is an organic compound and the acceptor component is a halogen. A minor proportion of graphite added to these composition helps reduce the resistivity.

  5. Sources and Information on Transfer Associate Degrees

    ERIC Educational Resources Information Center

    Ayon, Carlos

    2012-01-01

    This chapter provides an annotated bibliography of articles about the effects of transfer associate degrees and related statewide transfer and articulation policies. It also provides links to transfer degree legislation in several states.

  6. Near-infrared-induced electron transfer of an uranyl macrocyclic complex without energy transfer to dioxygen.

    PubMed

    Davis, Christina M; Ohkubo, Kei; Ho, I-Ting; Zhang, Zhan; Ishida, Masatoshi; Fang, Yuanyuan; Lynch, Vincent M; Kadish, Karl M; Sessler, Jonathan L; Fukuzumi, Shunichi

    2015-04-21

    Photoexcitation of dichloromethane solutions of an uranyl macrocyclic complex with cyclo[1]furan[1]pyridine[4]-pyrrole () at the near-infrared (NIR) band (1177 nm) in the presence of electron donors and acceptors resulted in NIR-induced electron transfer without producing singlet oxygen via energy transfer. PMID:25791126

  7. Information and complexity measures in molecular reactivity studies.

    PubMed

    Welearegay, Meressa A; Balawender, Robert; Holas, Andrzej

    2014-07-28

    The analysis of the information and complexity measures as tools for the investigation of the chemical reactivity has been done in the spin-position and the position spaces, for the density and shape representations. The concept of the transferability and additivity of atoms or functional groups were used as "checkpoints" in the analysis of obtained results. The shape function as an argument of various measures reveals less information than the spinor density. Use of the shape function can yield wrong conclusions when the information measures such as the Shannon entropy (SE, S), the Fisher information (FI, I), the Onicescu information (OI, D), and complexities based on them are used for the systems with different electron numbers. Results obtained in the spinor-density representation show the transferability and additivity (while lacking in the case of the shape representation). The group transferability is well illustrated in the example of the X-Y molecules and their benzene derivatives. Another example is the methyl group transferability presented on the alkane-alkene-alkyne set. Analysis of the results displayed on planes between the three information-theoretical (IT) based measures has shown that the S-I plane provides "richer" information about the pattern, organization, similarity of used molecules than the I-D and D-S planes. The linear relation of high accuracy is noted between the kinetic energy and the FI and the OI measures. Another interesting regression was found between the atomization total energy and the atomization entropy. Unfortunately, the lack of the group electronic energy transferability indicates that no general relations between the IT measures and the chemical reactivity indices are observed. The molecular set chosen for the study includes different types of molecules with various functional groups (19 groups). The used set is large enough (more than 700 molecules) and diverse to improve the previous understating of molecular complexities

  8. Photon-to-electron quantum information transfer

    NASA Astrophysics Data System (ADS)

    Kosaka, Hideo

    2011-05-01

    Spin is a fundamental property of electrons and plays an important role in information storage. For spin-based quantum information technology, preparation and read-out of the electron spin state must be spin coherent, but both the traditional preparation and read-out of the spin state are projective to up/down spin states, which do not have spin coherence. We have recently demonstrated that the polarization coherence of light can be coherently transferred to the spin coherence of electrons in a semiconductor. We have also developed a new scheme named tomographic Kerr rotation (TKR) by generalizing the traditional KR to directly readout the spin coherence of optically prepared electrons without the need for the spin dynamics, which allows the spin projection measurement in an arbitrary set of basis states. These demonstrations were performed using g-factor-controlled semiconductor quantum wells with precessing and nonprecessing electrons. The developed scheme offers a tool for performing basis-independent preparation and read-out of a spin quantum state in a solid. These results encourage us to make a quantum media converter between flying photon qubits and stationary electron spin qubits in semiconductors.

  9. Sources and Information: Revitalizing Articulation and Transfer.

    ERIC Educational Resources Information Center

    Palmer, James C.

    1982-01-01

    Reviews recent ERIC documents and journal articles dealing with the articulation and transfer process. Focuses on the status of the community college transfer function, the success of community college transfer students at four-year colleges, educational articulation, and experiential learning. Includes an extensive bibliography. (DMM)

  10. Free flap transfer for complex regional pain syndrome type II

    PubMed Central

    Matsuda, Ken; Kikuchi, Mamoru; Murase, Tsuyoshi; Hosokawa, Ko; Shibata, Minoru

    2014-01-01

    Abstract A patient with complex regional pain syndrome type II was successfully treated using free anterolateral thigh flap transfer with digital nerve coaptation to the cutaneous nerve of the flap. Release of the scarred tissue and soft tissue coverage with targeted sensory nerve coaptation were useful in relieving severe pain.

  11. Layered charge transfer complex cathodes or solid electrolyte cells

    SciTech Connect

    Louzos, D.V.

    1981-05-12

    Layered charge transfer complex cathodes for use in solid electrolyte cells are described wherein one layer of the cathode contains an electronic conductor which is isolated from the cell's solid electrolyte by a second layer of the cathode that does not contain an electronic conductor.

  12. Mapping energy transfer channels in fucoxanthin-chlorophyll protein complex.

    PubMed

    Gelzinis, Andrius; Butkus, Vytautas; Songaila, Egidijus; Augulis, Ramūnas; Gall, Andrew; Büchel, Claudia; Robert, Bruno; Abramavicius, Darius; Zigmantas, Donatas; Valkunas, Leonas

    2015-02-01

    Fucoxanthin-chlorophyll protein (FCP) is the key molecular complex performing the light-harvesting function in diatoms, which, being a major group of algae, are responsible for up to one quarter of the total primary production on Earth. These photosynthetic organisms contain an unusually large amount of the carotenoid fucoxanthin, which absorbs the light in the blue-green spectral region and transfers the captured excitation energy to the FCP-bound chlorophylls. Due to the large number of fucoxanthins, the excitation energy transfer cascades in these complexes are particularly tangled. In this work we present the two-color two-dimensional electronic spectroscopy experiments on FCP. Analysis of the data using the modified decay associated spectra permits a detailed mapping of the excitation frequency dependent energy transfer flow with a femtosecond time resolution. PMID:25445318

  13. 28 CFR 22.26 - Requests for transfer of information.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 28 Judicial Administration 1 2013-07-01 2013-07-01 false Requests for transfer of information. 22.26 Section 22.26 Judicial Administration DEPARTMENT OF JUSTICE CONFIDENTIALITY OF IDENTIFIABLE RESEARCH AND STATISTICAL INFORMATION § 22.26 Requests for transfer of information. (a) Requests...

  14. 28 CFR 22.26 - Requests for transfer of information.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 28 Judicial Administration 1 2012-07-01 2012-07-01 false Requests for transfer of information. 22.26 Section 22.26 Judicial Administration DEPARTMENT OF JUSTICE CONFIDENTIALITY OF IDENTIFIABLE RESEARCH AND STATISTICAL INFORMATION § 22.26 Requests for transfer of information. (a) Requests...

  15. 28 CFR 22.26 - Requests for transfer of information.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 28 Judicial Administration 1 2014-07-01 2014-07-01 false Requests for transfer of information. 22.26 Section 22.26 Judicial Administration DEPARTMENT OF JUSTICE CONFIDENTIALITY OF IDENTIFIABLE RESEARCH AND STATISTICAL INFORMATION § 22.26 Requests for transfer of information. (a) Requests...

  16. 28 CFR 22.26 - Requests for transfer of information.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 28 Judicial Administration 1 2010-07-01 2010-07-01 false Requests for transfer of information. 22.26 Section 22.26 Judicial Administration DEPARTMENT OF JUSTICE CONFIDENTIALITY OF IDENTIFIABLE RESEARCH AND STATISTICAL INFORMATION § 22.26 Requests for transfer of information. (a) Requests...

  17. 28 CFR 22.26 - Requests for transfer of information.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 28 Judicial Administration 1 2011-07-01 2011-07-01 false Requests for transfer of information. 22.26 Section 22.26 Judicial Administration DEPARTMENT OF JUSTICE CONFIDENTIALITY OF IDENTIFIABLE RESEARCH AND STATISTICAL INFORMATION § 22.26 Requests for transfer of information. (a) Requests...

  18. Histone octamer transfer by a chromatin-remodeling complex.

    PubMed

    Lorch, Y; Zhang, M; Kornberg, R D

    1999-02-01

    RSC, an abundant, essential chromatin-remodeling complex related to SWI/SNF complex, catalyzes the transfer of a histone octamer from a nucleosome core particle to naked DNA. The newly formed octamer-DNA complex is identical with a nucleosome in all respects. The reaction requires ATP and involves an activated RSC-nucleosome intermediate. The mechanism may entail formation of a duplex displacement loop on the nucleosome, facilitating the entry of exogeneous DNA and the release of the endogenous molecule. PMID:10025404

  19. Design Methodology of Long Complex Helium Cryogenic Transfer Lines

    NASA Astrophysics Data System (ADS)

    Fydrych, J.; Chorowski, M.; Polinski, J.; Skrzypacz, J.

    2010-04-01

    Big scientific facilities, like superconducting particle accelerators or fusion reactors require high cooling power, usually produced locally by large helium refrigerators and transferred, by means of liquid or supercritical helium, over the distances that may exceed several kilometres. Construction of cold helium transfer lines should take into consideration many different issues. The lines are exposed to thermal loads which can constitute an important part of the cryogenic system thermal budget. Pressure difference between the vacuum insulation and the inner content of the pipes causes significant mechanical stresses. The cyclic changes of temperature can lead to considerable fatigue stresses. Additionally, due to complex structure of the scientific facilities, the access to the cryogenic lines can be partly or totally limited. Therefore all these thermal and mechanical aspects have to be analyzed and compromised during the design phase of the complex helium transfer line. The paper presents a design methodology of long multi-channel helium cryogenic transfer lines. It describes some aspects of process line arrangement, thermo-mechanical calculation, supporting structure and contraction protection, taking as a case study cryogenic transfer line XATL1, dedicated for the Accelerator Module Test Facility (AMTF) of the European X-rays Free Electron Laser (XFEL).

  20. Manipulating the proton transfer process in molecular complexes: synthesis and spectroscopic studies.

    PubMed

    Panja, Sumit Kumar; Dwivedi, Nidhi; Saha, Satyen

    2016-08-01

    The proton transfer process in carefully designed molecular complexes has been investigated directly in the solid and solution phase. SCXRD studies have been employed to investigate the N-H-O bonding interaction sites of the molecular complexes, with additional experimental support from FTIR and Raman spectroscopic studies, to gain information on the relative position of hydrogen in between the N and O centers. Further, the proton transfer process in solution is studied using UV-Visible spectroscopy through monitoring the intramolecular charge transfer (ICT) process in these molecular complexes, which is primarily governed by the number of electron withdrawing groups (nitro groups) on proton donor moieties (NP, DNP and TNP). It is found that the magnitude of the ICT process depends on the extent of proton transfer, which on the other hand depends on the relative stabilities of the constituent species (phenolate species). A correlation is observed between an increase in the number of nitro groups and an increase in the melting point of the molecular complexes, indicating the enhancement of ionic character due to the proton transfer process. The aliphatic H-bonding is identified and monitored using (1)H-NMR spectroscopy, which reveals that the identity of molecular complexes in solution interestingly depends on the extent of proton transfer, in addition to the nature of the solvents. The aliphatic C-H-O H-bonding interaction between the oxygen atom of the nitro group and the alkyl hydrogen in piperidinium was also found to play a significant role in strengthening the primary interaction involving a hydrogen transfer process. The conductivity of the molecular complexes increases with an increase in the number of nitro groups, indicating the enhancement in ionic character of the molecular complexes. PMID:27424765

  1. Photoinduced energy transfer in transition metal complex oligomers

    SciTech Connect

    1997-06-01

    The work done over the past three years has been directed toward the preparation, characterization and photophysical examination of mono- and bimetallic diimine complexes. The work is part of a broader project directed toward the development of stable, efficient, light harvesting arrays of transition metal complex chromophores. One focus has been the synthesis of rigid bis-bidentate and bis-tridentate bridging ligands. The authors have managed to make the ligand bphb in multigram quantities from inexpensive starting materials. The synthetic approach used has allowed them to prepare a variety of other ligands which may have unique applications (vide infra). They have prepared, characterized and examined the photophysical behavior of Ru(II) and Re(I) complexes of the ligands. Energy donor/acceptor complexes of bphb have been prepared which exhibit nearly activationless energy transfer. Complexes of Ru(II) and Re(I) have also been prepared with other polyunsaturated ligands in which two different long lived (> 50 ns) excited states exist; results of luminescence and transient absorbance measurements suggest the two states are metal-to-ligand charge transfer and ligand localized {pi}{r_arrow}{pi}* triplets. Finally, the authors have developed methods to prepare polymetallic complexes which are covalently bound to various surfaces. The long term objective of this work is to make light harvesting arrays for the sensitization of large band gap semiconductors. Details of this work are provided in the body of the report.

  2. Photoinduced energy transfer in transition metal complex oligomers

    SciTech Connect

    1997-04-01

    The work we have done over the past three years has been directed toward the preparation, characterization and photophysical examination of mono- and bimetallic diimine complexes. The work is part of a broader project directed toward the development of stable, efficient, light harvesting arrays of transition metal complex chromophores. One focus has been the synthesis of rigid bis-bidentate and bis-tridentate bridging ligands. We have managed to make the ligand bphb in multigram quantities from inexpensive starting materials. The synthetic approach used has allowed us prepare a variety of other ligands which may have unique applications (vide infra). We have prepared, characterized and examined the photophysical behavior of Ru(II) and Re(I) complexes of the ligands. Energy donor/acceptor complexes of bphb have been prepared which exhibit nearly activationless energy transfer. Complexes of Ru(II) and Re(I) have also been prepared with other polyunsaturated ligands in which two different long lived ( > 50 ns) excited states exist; results of luminescence and transient absorbance measurements suggest the two states are metal-to-ligand charge transfer and ligand localized {pi}{r_arrow}{pi}* triplets. Finally, we have developed methods to prepare polymetallic complexes which are covalently bound to various surfaces. The long term objective of this work is to make light harvesting arrays for the sensitization of large band gap semiconductors. Details of this work are provided in the body of the report.

  3. Revealing the complex conduction heat transfer mechanism of nanofluids.

    PubMed

    Sergis, A; Hardalupas, Y

    2015-12-01

    Nanofluids are two-phase mixtures consisting of small percentages of nanoparticles (sub 1-10 %vol) inside a carrier fluid. The typical size of nanoparticles is less than 100 nm. These fluids have been exhibiting experimentally a significant increase of thermal performance compared to the corresponding carrier fluids, which cannot be explained using the classical thermodynamic theory. This study deciphers the thermal heat transfer mechanism for the conductive heat transfer mode via a molecular dynamics simulation code. The current findings are the first of their kind and conflict with the proposed theories for heat transfer propagation through micron-sized slurries and pure matter. The authors provide evidence of a complex new type of heat transfer mechanism, which explains the observed abnormal heat transfer augmentation. The new mechanism appears to unite a number of popular speculations for the thermal heat transfer mechanism employed by nanofluids as predicted by the majority of the researchers of the field into a single one. The constituents of the increased diffusivity of the nanoparticle can be attributed to mismatching of the local temperature profiles between parts of the surface of the solid and the fluid resulting in increased local thermophoretic effects. These effects affect the region surrounding the solid manifesting interfacial layer phenomena (Kapitza resistance). In this region, the activity of the fluid and the interactions between the fluid and the nanoparticle are elevated. Isotropic increased nanoparticle mobility is manifested as enhanced Brownian motion and diffusion effects. PMID:26058515

  4. Revealing the complex conduction heat transfer mechanism of nanofluids

    NASA Astrophysics Data System (ADS)

    Sergis, A.; Hardalupas, Y.

    2015-06-01

    Nanofluids are two-phase mixtures consisting of small percentages of nanoparticles (sub 1-10 %vol) inside a carrier fluid. The typical size of nanoparticles is less than 100 nm. These fluids have been exhibiting experimentally a significant increase of thermal performance compared to the corresponding carrier fluids, which cannot be explained using the classical thermodynamic theory. This study deciphers the thermal heat transfer mechanism for the conductive heat transfer mode via a molecular dynamics simulation code. The current findings are the first of their kind and conflict with the proposed theories for heat transfer propagation through micron-sized slurries and pure matter. The authors provide evidence of a complex new type of heat transfer mechanism, which explains the observed abnormal heat transfer augmentation. The new mechanism appears to unite a number of popular speculations for the thermal heat transfer mechanism employed by nanofluids as predicted by the majority of the researchers of the field into a single one. The constituents of the increased diffusivity of the nanoparticle can be attributed to mismatching of the local temperature profiles between parts of the surface of the solid and the fluid resulting in increased local thermophoretic effects. These effects affect the region surrounding the solid manifesting interfacial layer phenomena (Kapitza resistance). In this region, the activity of the fluid and the interactions between the fluid and the nanoparticle are elevated. Isotropic increased nanoparticle mobility is manifested as enhanced Brownian motion and diffusion effects

  5. The coordination and atom transfer chemistry of titanium porphyrin complexes

    SciTech Connect

    Hays, J.A.

    1993-11-05

    Preparation, characterization, and reactivity of ({eta}{sup 2}- alkyne)(meso-tetratolylpoprphrinato)titanium(II) complexes are described, along with inetermetal oxygen atom transfer reactions involving Ti(IV) and Ti(III) porphyrin complexes. The {eta}{sup 2}- alkyne complexes are prepared by reaction of (TTP)TiCl{sub 2} with LiAlH{sub 4} in presence of alkyne. Structure of (OEP)Ti({eta}{sup 2}-Ph-C{triple_bond}C-Ph) (OEP=octaethylporphryin) was determined by XRD. The compounds undergo simple substitution to displace the alkyne and produce doubly substituted complexes. Structure of (TTP)Ti(4-picoline){sub 2} was also determined by XRD. Reaction of (TTP)Ti{double_bond}O with (OEP)Ti-Cl yields intermetal O/Cl exchange, which is a one-electron redox process mediated by O atom transfer. Also a zero-electron redox process mediated by atom transfer is observed when (TTP)TiCl{sub 2} is reacted with (OEP)Ti{double_bond}O.

  6. 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

  7. Recording information on protein complexes in an information management system

    PubMed Central

    Savitsky, Marc; Diprose, Jonathan M.; Morris, Chris; Griffiths, Susanne L.; Daniel, Edward; Lin, Bill; Daenke, Susan; Bishop, Benjamin; Siebold, Christian; Wilson, Keith S.; Blake, Richard; Stuart, David I.; Esnouf, Robert M.

    2011-01-01

    The Protein Information Management System (PiMS) is a laboratory information management system (LIMS) designed for use with the production of proteins in a research environment. The software is distributed under the CCP4 licence, and so is available free of charge to academic laboratories. Like most LIMS, the underlying PiMS data model originally had no support for protein–protein complexes. To support the SPINE2-Complexes project the developers have extended PiMS to meet these requirements. The modifications to PiMS, described here, include data model changes, additional protocols, some user interface changes and functionality to detect when an experiment may have formed a complex. Example data are shown for the production of a crystal of a protein complex. Integration with SPINE2-Complexes Target Tracker application is also described. PMID:21605682

  8. Dimensions of the information transfer problem. [human performance

    NASA Technical Reports Server (NTRS)

    Billings, C. E.; Reynard, W. D.

    1981-01-01

    Several facets of the information transfer problems in aviation are described. A general analysis of these problem are given and the implications of some proposed solutions discussed. It is concluded that information transfer problems are responsible for many potentially serious human errors in aviation operations.

  9. Year 7 Students, Information Literacy, and Transfer: A Grounded Theory

    ERIC Educational Resources Information Center

    Herring, James E.

    2011-01-01

    This study examined the views of year 7 students, teacher librarians, and teachers in three state secondary schools in rural New South Wales, Australia, on information literacy and transfer. The aims of the study included the development of a grounded theory in relation to information literacy and transfer in these schools. The study's perspective…

  10. Charge-transfer complexes of phenylephrine with nitrobenzene derivatives

    NASA Astrophysics Data System (ADS)

    El-Mossalamy, E. H.

    2004-04-01

    The molecular charge-transfer complexes of phenylephrine with picric acid and m-dinitrobenzene have been studied and investigated by IR, 1H NMR electronic spectra in organic solvents and buffer solutions, respectively. Simple and selective methods are proposed for the determination of phenylephrine hydrochloride in bulk form and in tablets. The two methods are based on the formation of charge-transfer complexes between drug base as a n-donor (D) and picric acid, m-dinitrobenzene as π-acceptor (A). The products exhibit absorption maxima at 497 and 560 nm in acetonitrile for picric acid and m-dinitrobenzene, respectively. The coloured product exhibits an absorption maximum at 650 nm in dioxane. The sensitive kinetic methods for the determination phynylephrine hydrochloride are described. The method is based upon a kinetic investigation of the oxidation reaction of the drug with alkaline potassium permanganate at room temperature for a fixed time at 20 min.

  11. Light induced electron transfer reactions of metal complexes

    SciTech Connect

    Sutin, N.; Creutz, C.

    1980-01-01

    Properties of the excited states of tris(2,2'-bipyridine) and tris(1,10-phenanthroline) complexes of chromium(III), iron(II), ruthenium(II), osmium(II), rhodium(III), and iridium(III) are described. The electron transfer reactions of the ground and excited states are discussed and interpreted in terms of the driving force for the reaction and the distortions of the excited states relative to the corresponding ground states. General considerations relevant to the conversion of light into chemical energy are presented and progress in the use of polypyridine complexes to effect the light decomposition of water into hydrogen and oxygen is reviewed.

  12. Eeg Transfer Entropy Tracks Changes in Information Transfer on the Onset of Vision

    NASA Astrophysics Data System (ADS)

    Madulara, M. D.; Francisco, P. A. B.; Nawang, S.; Arogancia, D. C.; Cellucci, C. J.; Rapp, P. E.; Albano, A. M.

    We investigate the pairwise mutual information and transfer entropy of ten-channel, free-running electroencephalographs measured from thirteen subjects under two behavioral conditions: eyes open resting and eyes closed resting. Mutual information measures nonlinear correlations; transfer entropy determines the directionality of information transfer. For all channel pairs, mutual information is generally lower with eyes open compared to eyes closed indicating that EEG signals at different scalp sites become more dissimilar as the visual system is engaged. On the other hand, transfer entropy increases on average by almost two-fold when the eyes are opened. The largest one-way transfer entropies are to and from the Oz site consistent with the involvement of the occipital lobe in vision. The largest net transfer entropies are from F3 and F4 to almost all the other scalp sites.

  13. Transfer of Complex Skill Learning from Virtual to Real Rowing

    PubMed Central

    Rauter, Georg; Sigrist, Roland; Koch, Claudio; Crivelli, Francesco; van Raai, Mark; Riener, Robert; Wolf, Peter

    2013-01-01

    Simulators are commonly used to train complex tasks. In particular, simulators are applied to train dangerous tasks, to save costs, and to investigate the impact of different factors on task performance. However, in most cases, the transfer of simulator training to the real task has not been investigated. Without a proof for successful skill transfer, simulators might not be helpful at all or even counter-productive for learning the real task. In this paper, the skill transfer of complex technical aspects trained on a scull rowing simulator to sculling on water was investigated. We assume if a simulator provides high fidelity rendering of the interactions with the environment even without augmented feedback, training on such a realistic simulator would allow similar skill gains as training in the real environment. These learned skills were expected to transfer to the real environment. Two groups of four recreational rowers participated. One group trained on water, the other group trained on a simulator. Within two weeks, both groups performed four training sessions with the same licensed rowing trainer. The development in performance was assessed by quantitative biomechanical performance measures and by a qualitative video evaluation of an independent, blinded trainer. In general, both groups could improve their performance on water. The used biomechanical measures seem to allow only a limited insight into the rowers' development, while the independent trainer could also rate the rowers' overall impression. The simulator quality and naturalism was confirmed by the participants in a questionnaire. In conclusion, realistic simulator training fostered skill gains to a similar extent as training in the real environment and enabled skill transfer to the real environment. In combination with augmented feedback, simulator training can be further exploited to foster motor learning even to a higher extent, which is subject to future work. PMID:24376518

  14. Transfer of complex skill learning from virtual to real rowing.

    PubMed

    Rauter, Georg; Sigrist, Roland; Koch, Claudio; Crivelli, Francesco; van Raai, Mark; Riener, Robert; Wolf, Peter

    2013-01-01

    Simulators are commonly used to train complex tasks. In particular, simulators are applied to train dangerous tasks, to save costs, and to investigate the impact of different factors on task performance. However, in most cases, the transfer of simulator training to the real task has not been investigated. Without a proof for successful skill transfer, simulators might not be helpful at all or even counter-productive for learning the real task. In this paper, the skill transfer of complex technical aspects trained on a scull rowing simulator to sculling on water was investigated. We assume if a simulator provides high fidelity rendering of the interactions with the environment even without augmented feedback, training on such a realistic simulator would allow similar skill gains as training in the real environment. These learned skills were expected to transfer to the real environment. Two groups of four recreational rowers participated. One group trained on water, the other group trained on a simulator. Within two weeks, both groups performed four training sessions with the same licensed rowing trainer. The development in performance was assessed by quantitative biomechanical performance measures and by a qualitative video evaluation of an independent, blinded trainer. In general, both groups could improve their performance on water. The used biomechanical measures seem to allow only a limited insight into the rowers' development, while the independent trainer could also rate the rowers' overall impression. The simulator quality and naturalism was confirmed by the participants in a questionnaire. In conclusion, realistic simulator training fostered skill gains to a similar extent as training in the real environment and enabled skill transfer to the real environment. In combination with augmented feedback, simulator training can be further exploited to foster motor learning even to a higher extent, which is subject to future work. PMID:24376518

  15. Exploiting Complexity Information for Brain Activation Detection

    PubMed Central

    Zhang, Yan; Liang, Jiali; Lin, Qiang; Hu, Zhenghui

    2016-01-01

    We present a complexity-based approach for the analysis of fMRI time series, in which sample entropy (SampEn) is introduced as a quantification of the voxel complexity. Under this hypothesis the voxel complexity could be modulated in pertinent cognitive tasks, and it changes through experimental paradigms. We calculate the complexity of sequential fMRI data for each voxel in two distinct experimental paradigms and use a nonparametric statistical strategy, the Wilcoxon signed rank test, to evaluate the difference in complexity between them. The results are compared with the well known general linear model based Statistical Parametric Mapping package (SPM12), where a decided difference has been observed. This is because SampEn method detects brain complexity changes in two experiments of different conditions and the data-driven method SampEn evaluates just the complexity of specific sequential fMRI data. Also, the larger and smaller SampEn values correspond to different meanings, and the neutral-blank design produces higher predictability than threat-neutral. Complexity information can be considered as a complementary method to the existing fMRI analysis strategies, and it may help improving the understanding of human brain functions from a different perspective. PMID:27045838

  16. Exploiting Complexity Information for Brain Activation Detection.

    PubMed

    Zhang, Yan; Liang, Jiali; Lin, Qiang; Hu, Zhenghui

    2016-01-01

    We present a complexity-based approach for the analysis of fMRI time series, in which sample entropy (SampEn) is introduced as a quantification of the voxel complexity. Under this hypothesis the voxel complexity could be modulated in pertinent cognitive tasks, and it changes through experimental paradigms. We calculate the complexity of sequential fMRI data for each voxel in two distinct experimental paradigms and use a nonparametric statistical strategy, the Wilcoxon signed rank test, to evaluate the difference in complexity between them. The results are compared with the well known general linear model based Statistical Parametric Mapping package (SPM12), where a decided difference has been observed. This is because SampEn method detects brain complexity changes in two experiments of different conditions and the data-driven method SampEn evaluates just the complexity of specific sequential fMRI data. Also, the larger and smaller SampEn values correspond to different meanings, and the neutral-blank design produces higher predictability than threat-neutral. Complexity information can be considered as a complementary method to the existing fMRI analysis strategies, and it may help improving the understanding of human brain functions from a different perspective. PMID:27045838

  17. Entropy Transfer of Quantum Gravity Information Processing

    NASA Astrophysics Data System (ADS)

    Gyongyosi, Laszlo; Imre, Sandor

    2015-05-01

    We introduce the term smooth entanglement entropy transfer, a phenomenon that is a consequence of the causality-cancellation property of the quantum gravity environment. The causality-cancellation of the quantum gravity space removes the causal dependencies of the local systems. We study the physical effects of the causality-cancellation and show that it stimulates entropy transfer between the quantum gravity environment and the independent local systems of the quantum gravity space. The entropy transfer reduces the entropies of the contributing local systems and increases the entropy of the quantum gravity environment. We discuss the space-time geometry structure of the quantum gravity environment and the local quantum systems. We propose the space-time geometry model of the smooth entropy transfer. We reveal on a smooth Cauchy slice that the space-time geometry of the quantum gravity environment dynamically adapts to the vanishing causality. We prove that the Cauchy area expansion, along with the dilation of the Rindler horizon area of the quantum gravity environment, is a corollary of the causality-cancellation of the quantum gravity environment. This work was partially supported by the GOP-1.1.1-11-2012-0092 (Secure quantum key distribution between two units on optical fiber network) project sponsored by the EU and European Structural Fund, and by the COST Action MP1006.

  18. Information transfer satellite concept study. Volume 3: Appendices

    NASA Technical Reports Server (NTRS)

    Bergin, P.; Kincade, C.; Kurpiewski, D.; Leinhaupel, F.; Millican, F.; Onstad, R.

    1971-01-01

    Briefly reviewed are the various documents which supply background information for the information transfer satellite study. The sixteen papers reviewed are evaluated in terms of: (1) the category of service or demand being treated; (2) the extent to which information transfer predictions are quantified; (3) the degree to which the data supplied is adequate for the purposes of system synthesis; (4) some assessment as to the overall utility of the data presented in the paper.

  19. Presentation Media, Information Complexity, and Learning Outcomes

    ERIC Educational Resources Information Center

    Andres, Hayward P.; Petersen, Candice

    2002-01-01

    Cognitive processing limitations restrict the number of complex information items held and processed in human working memory. To overcome such limitations, a verbal working memory channel is used to construct an if-then proposition representation of facts and a visual working memory channel is used to construct a visual imagery of geometric…

  20. Electronic Energy transfer in light-harvesting antenna complexes

    NASA Astrophysics Data System (ADS)

    Hossein-Nejad, Hoda

    The studies presented in this thesis explore electronic energy transfer (EET) in light-harvesting antenna complexes and investigate the role of quantum coherence in EET. The dynamics of energy transfer are investigated in three distinct length scales and a different formulation of the exciton transport problem is applied at each scale. These scales include: the scale of a molecular dimer, the scale of a single protein and the scale of a molecular aggregate. The antenna protein phycoerythrin 545 (PE545) isolated from the photosynthetic cryptophyte algae Rhodomonas CS4 is specifically studied in two chapters of this thesis. It is found that formation of small aggregates delocalizes the excitation across chromophores of adjacent proteins, and that this delocalization has a dramatic effect in enhancing the rate of energy transfer between pigments. Furthermore, we investigate EET from a donor to an acceptor via an intermediate site and observe that interference of coherent pathways gives a finite correction to the transfer rate that is sensitively dependent on the nature of the vibrational interactions in the system. The statistical fluctuations of a system exhibiting EET are investigated in the final chapter. The techniques of non-equilibrium statistical mechanics are applied to investigate the steady-state of a typical system exhibiting EET that is perturbed out of equilibrium due to its interaction with a fluctuating bath.

  1. Electron Transfer Reactions in Colloidal Quantum Dot-Ligand Complexes

    NASA Astrophysics Data System (ADS)

    Morris-Cohen, Adam Joshua

    This thesis describes a quantitative analysis of the chemical composition of colloidal II-VI quantum dot (QD)-ligand complexes and transient absorption experiments analyzing the rates of electron transfer reactions in these complexes functionalized with redox active ligands. Chemical analysis reveals that phosphonate impurities in the surfactants used to synthesize CdSe QDs are the dominant ligands on the surface of the QDs, and these phosphonate impurities cause size-dependent Cd-enrichment of the QD surface. A study of the adsorption equilibrium of solution-phase CdS quantum dots and acid-derivatized viologen ligands (V2+) reveals that the structure of the surfaces of the QDs depends on the concentration of the QDs. A new model based on the Langmuir isotherm that treats both the number of adsorbed ligands per QD and the number of available binding sites per QD as binomially-distributed quantities is described. Transient absorption spectroscopy of solution-phase mixtures of colloidal CdS QDs and V2+ indicates electron transfer occurs from the conduction band of the QD to the LUMO of V2+. The rate constant for photoinduced electron transfer (PET) is independent of the number of methylene groups in the alkyl chain on the acid-derivatized viologen. The insensitivity of the electron transfer rate constant to the length of the functional groups on the viologen suggests a van der Waals (vdW) pathway for PET, where the electron bypasses the alkylcarboxylate and tunnels through the orbitals of the QD and of the bipyridinium core. The rate of PET from colloidal CdSe quantum dots (QDs) to oxo-centered triruthenium clusters (Ru 3O) depends on the structure of the chemical headgroup by which the Ru3O clusters adsorb to the QDs. Complexes comprising QDs and Ru 3O clusters adsorbed through a pyridine-4-carboxylic acid ligand have a PET rate constant of (4.9 ± 0.9)×109 s -1 whereas complexes comprising QDs and Ru3O clusters adsorbed through a 4-mercaptopyridine ligand have an

  2. Modelling excitonic-energy transfer in light-harvesting complexes

    SciTech Connect

    Kramer, Tobias; Kreisbeck, Christoph

    2014-01-08

    The theoretical and experimental study of energy transfer in photosynthesis has revealed an interesting transport regime, which lies at the borderline between classical transport dynamics and quantum-mechanical interference effects. Dissipation is caused by the coupling of electronic degrees of freedom to vibrational modes and leads to a directional energy transfer from the antenna complex to the target reaction-center. The dissipative driving is robust and does not rely on fine-tuning of specific vibrational modes. For the parameter regime encountered in the biological systems new theoretical tools are required to directly compare theoretical results with experimental spectroscopy data. The calculations require to utilize massively parallel graphics processor units (GPUs) for efficient and exact computations.

  3. Infrared Spectroscopy of Charge Transfer Complexes of Purines and Pyrimidines

    SciTech Connect

    Rathod, Pravinsinh I.; Oza, A. T.

    2011-10-20

    The FTIR spectra of charge transfer complexes of purines and pyrimidines with organic acceptors such as TCNQ, TCNE, DDQ, chloranil and iodine are obtained and studied in the present work. Adenine, guanine, thymine, cytosine and uracil are the purines and pyrimidines which are found as constituent of DNA and RNA. Charge transfer induced hydrogen bonding is concluded on the basis of indirect transitions observed in the infrared range in these CTCs. Some CTCs show gaussian bands revealing delocalization of charge carriers. The CTCs show interband transition in three-dimensions rather than two-dimensions unlike CTCs of amino acids. There is no extended hydrogen bonded network spanning the whole crystal. This leads to indirect transition due to locally deformed lattice furnishing a phonon-assisted transition.

  4. Feedback Specificity, Information Processing, and Transfer of Training

    ERIC Educational Resources Information Center

    Goodman, Jodi S.; Wood, Robert E.; Chen, Zheng

    2011-01-01

    This study examines the effects of feedback specificity on transfer of training and the mechanisms through which feedback can enhance or inhibit transfer. We used concurrent verbal protocol methodology to elicit and operationalize the explicit information processing activities used by 48 trainees performing the Furniture Factory computer…

  5. A flight test facility design for examining digital information transfer

    NASA Technical Reports Server (NTRS)

    Knox, Charles E.

    1990-01-01

    Information is given in viewgraph form on a flight test facility design for examining digital information transfer. Information is given on aircraft/ground exchange, data link research activities, data link display format, a data link flight test, and the flight test setup.

  6. Information Systems and Networks for Technology Transfer. Final Report.

    ERIC Educational Resources Information Center

    Page, John; Szentivanyi, Tibor

    Results of a survey of the information resources available in industrialized countries which might be used in a United Nations technology transfer program for developing countries are presented. Information systems and networks, organized information collections of a scientific and technical character, and the machinery used to disseminate this…

  7. Efficient information transfer by Poisson neurons.

    PubMed

    Kostal, Lubomir; Shinomoto, Shigeru

    2016-06-01

    Recently, it has been suggested that certain neurons with Poissonian spiking statistics may communicate by discontinuously switching between two levels of firing intensity. Such a situation resembles in many ways the optimal information transmission protocol for the continuous-time Poisson channel known from information theory. In this contribution we employ the classical information-theoretic results to analyze the efficiency of such a transmission from different perspectives, emphasising the neurobiological viewpoint. We address both the ultimate limits, in terms of the information capacity under metabolic cost constraints, and the achievable bounds on performance at rates below capacity with fixed decoding error probability. In doing so we discuss optimal values of experimentally measurable quantities that can be compared with the actual neuronal recordings in a future effort. PMID:27106184

  8. Optimal information transfer in the cortex through synchronization.

    PubMed

    Buehlmann, Andres; Deco, Gustavo

    2010-01-01

    In recent experimental work it has been shown that neuronal interactions are modulated by neuronal synchronization and that this modulation depends on phase shifts in neuronal oscillations. This result suggests that connections in a network can be shaped through synchronization. Here, we test and expand this hypothesis using a model network. We use transfer entropy, an information theoretical measure, to quantify the exchanged information. We show that transferred information depends on the phase relation of the signal, that the amount of exchanged information increases as a function of oscillations in the signal and that the speed of the information transfer increases as a function of synchronization. This implies that synchronization makes information transport more efficient. In summary, our results reinforce the hypothesis that synchronization modulates neuronal interactions and provide further evidence that gamma band synchronization has behavioral relevance. PMID:20862355

  9. Magnetic ordering in fullerene charge-transfer complexes

    NASA Astrophysics Data System (ADS)

    Sato, Tohru; Yamabe, Tokio; Tanaka, Kazuyoshi

    1997-07-01

    We have determined the ground states of the charge-transfer (CT) complexes in which the energy levels of the highest occupied molecular orbital (HOMO) of donors and the lowest unoccupied MO (LUMO) of acceptors are closely located, and examined some fullerene complexes consisting of C60, C70, tetrakis(dimethylamino)ethylene (TDAE), and 1,1',3,3'-tetramethyl-Δ2,2'-bi(imidazolidine) (TMBI). The observed magnetic properties of TDAE-C60, TMBI-C60, and TDAE-C70 can be accounted for by employing realistic parameters. The effective Hamiltonian including up to the fourth-order perturbation has also been derived in the fourfold degenerate model space. The effective Hamiltonian can plausibly reproduce the magnetic phase diagram obtained by the variational treatment of TDAE-C60. It has been shown that the third and the fourth processes contribute to the stabilization of the antiferromagnetic state.

  10. Information, complexity and efficiency: The automobile model

    SciTech Connect

    Allenby, B. |

    1996-08-08

    The new, rapidly evolving field of industrial ecology - the objective, multidisciplinary study of industrial and economic systems and their linkages with fundamental natural systems - provides strong ground for believing that a more environmentally and economically efficient economy will be more information intensive and complex. Information and intellectual capital will be substituted for the more traditional inputs of materials and energy in producing a desirable, yet sustainable, quality of life. While at this point this remains a strong hypothesis, the evolution of the automobile industry can be used to illustrate how such substitution may, in fact, already be occurring in an environmentally and economically critical sector.

  11. Forest Resource Information System. Phase 3: System transfer report

    NASA Technical Reports Server (NTRS)

    Mroczynski, R. P. (Principal Investigator)

    1981-01-01

    Transfer of the forest reserve information system (FRIS) from the Laboratory for Applications of Remote Sensing to St. Regis Paper Company is described. Modifications required for the transfer of the LARYS image processing software are discussed. The reformatting, geometric correction, image registration, and documentation performed for preprocessing transfer are described. Data turnaround was improved and geometrically corrected and ground-registered CCT LANDSAT 3 data provided to the user. The technology transfer activities are summarized. An application test performed in order to assess a Florida land acquisition is described. A benefit/cost analysis of FRIS is presented.

  12. Maximizing information exchange between complex networks

    NASA Astrophysics Data System (ADS)

    West, Bruce J.; Geneston, Elvis L.; Grigolini, Paolo

    2008-10-01

    modern research overarching all of the traditional scientific disciplines. The transportation networks of planes, highways and railroads; the economic networks of global finance and stock markets; the social networks of terrorism, governments, businesses and churches; the physical networks of telephones, the Internet, earthquakes and global warming and the biological networks of gene regulation, the human body, clusters of neurons and food webs, share a number of apparently universal properties as the networks become increasingly complex. Ubiquitous aspects of such complex networks are the appearance of non-stationary and non-ergodic statistical processes and inverse power-law statistical distributions. Herein we review the traditional dynamical and phase-space methods for modeling such networks as their complexity increases and focus on the limitations of these procedures in explaining complex networks. Of course we will not be able to review the entire nascent field of network science, so we limit ourselves to a review of how certain complexity barriers have been surmounted using newly applied theoretical concepts such as aging, renewal, non-ergodic statistics and the fractional calculus. One emphasis of this review is information transport between complex networks, which requires a fundamental change in perception that we express as a transition from the familiar stochastic resonance to the new concept of complexity matching.

  13. Electron transfer dissociation of dipositive uranyl and plutonyl coordination complexes.

    PubMed

    Rios, Daniel; Rutkowski, Philip X; Shuh, David K; Bray, Travis H; Gibson, John K; Van Stipdonk, Michael J

    2011-12-01

    Reported here is a comparison of electron transfer dissociation (ETD) and collision-induced dissociation (CID) of solvent-coordinated dipositive uranyl and plutonyl ions generated by electrospray ionization. Fundamental differences between the ETD and CID processes are apparent, as are differences between the intrinsic chemistries of uranyl and plutonyl. Reduction of both charge and oxidation state, which is inherent in ETD activation of [An(VI) O(2) (CH(3) COCH(3) )(4) ](2+) , [An(VI) O(2) (CH(3) CN)(4) ](2) , [U(VI) O(2) (CH(3) COCH(3) )(5) ](2+) and [U(VI) O(2) (CH(3) CN)(5) ](2+) (An = U or Pu), is accompanied by ligand loss. Resulting low-coordinate uranyl(V) complexes add O(2) , whereas plutonyl(V) complexes do not. In contrast, CID of the same complexes generates predominantly doubly-charged products through loss of coordinating ligands. Singly-charged CID products of [U(VI) O(2) (CH(3) COCH(3) )(4,5) ](2+) , [U(VI) O(2) (CH(3) CN)(4,5) ](2+) and [Pu(VI) O(2) (CH(3) CN)(4) ](2+) retain the hexavalent metal oxidation state with the addition of hydroxide or acetone enolate anion ligands. However, CID of [Pu(VI) O(2) (CH(3) COCH(3) )(4) ](2+) generates monopositive plutonyl(V) complexes, reflecting relatively more facile reduction of Pu(VI) to Pu(V). PMID:22223415

  14. Redundant and synergistic information transfer in cardiovascular and cardiorespiratory variability.

    PubMed

    Faes, Luca; Porta, Alberto; Nollo, Giandomenico

    2015-08-01

    In the framework of information dynamics, new tools are emerging which allow one to quantify how the information provided by two source processes about a target process results from the contribution of each source and from the interaction between the sources. We present the first implementation of these tools in the assessment of short-term cardiovascular and cardiorespiratory variability, by introducing two strategies for the decomposition of the information transferred to heart period (HP) variability from systolic arterial pressure (SAP) and respiration flow (RF) variability. Several measures based on the notion of transfer entropy (TE) are defined to quantify joint, individual and redundant/synergistic information transfer, and are then estimated from the series of HP, SAP and RF obtained from healthy subjects during head-up tilt and paced breathing protocols. Our results show that the proposed information decomposition methods provide an enhanced view on cardiovascular and cardiorespiratory regulation. PMID:26737179

  15. Quantum information transfer between topological and conventional charge qubits

    NASA Astrophysics Data System (ADS)

    Jun, Li; Yan, Zou

    2016-02-01

    We propose a scheme to realize coherent quantum information transfer between topological and conventional charge qubits. We first consider a hybrid system where a quantum dot (QD) is tunnel-coupled to a semiconductor Majorana-hosted nanowire (MNW) via using gated control as a switch, the information encoded in the superposition state of electron empty and occupied state can be transferred to each other through choosing the proper interaction time to make measurements. Then we consider another system including a double QDs and a pair of parallel MNWs, it is shown that the entanglement information transfer can be realized between the two kinds of systems. We also realize long distance quantum information transfer between two quantum dots separated by an MNW, by making use of the nonlocal fermionic level formed with the pared Majorana feimions (MFs) emerging at the two ends of the MNW. Furthermore, we analyze the teleportationlike electron transfer phenomenon predicted by Tewari et al. [Phys. Rev. Lett. 100, 027001 (2008)] in our considered system. Interestingly, we find that this phenomenon exactly corresponds to the case that the information encoded in one QD just returns back to its original place during the dynamical evolution of the combined system from the perspective of quantum state transfer. Project supported by the National Natural Science Foundation of China (Grant No. 11304031).

  16. Informational analysis involving application of complex information system

    NASA Astrophysics Data System (ADS)

    Ciupak, Clébia; Vanti, Adolfo Alberto; Balloni, Antonio José; Espin, Rafael

    The aim of the present research is performing an informal analysis for internal audit involving the application of complex information system based on fuzzy logic. The same has been applied in internal audit involving the integration of the accounting field into the information systems field. The technological advancements can provide improvements to the work performed by the internal audit. Thus we aim to find, in the complex information systems, priorities for the work of internal audit of a high importance Private Institution of Higher Education. The applied method is quali-quantitative, as from the definition of strategic linguistic variables it was possible to transform them into quantitative with the matrix intersection. By means of a case study, where data were collected via interview with the Administrative Pro-Rector, who takes part at the elaboration of the strategic planning of the institution, it was possible to infer analysis concerning points which must be prioritized at the internal audit work. We emphasize that the priorities were identified when processed in a system (of academic use). From the study we can conclude that, starting from these information systems, audit can identify priorities on its work program. Along with plans and strategic objectives of the enterprise, the internal auditor can define operational procedures to work in favor of the attainment of the objectives of the organization.

  17. Gating of single molecule junction conductance by charge transfer complex formation

    NASA Astrophysics Data System (ADS)

    Vezzoli, Andrea; Grace, Iain; Brooke, Carly; Wang, Kun; Lambert, Colin J.; Xu, Bingqian; Nichols, Richard J.; Higgins, Simon J.

    2015-11-01

    The solid-state structures of organic charge transfer (CT) salts are critical in determining their mode of charge transport, and hence their unusual electrical properties, which range from semiconducting through metallic to superconducting. In contrast, using both theory and experiment, we show here that the conductance of metal |single molecule| metal junctions involving aromatic donor moieties (dialkylterthiophene, dialkylbenzene) increase by over an order of magnitude upon formation of charge transfer (CT) complexes with tetracyanoethylene (TCNE). This enhancement occurs because CT complex formation creates a new resonance in the transmission function, close to the metal contact Fermi energy, that is a signal of room-temperature quantum interference.The solid-state structures of organic charge transfer (CT) salts are critical in determining their mode of charge transport, and hence their unusual electrical properties, which range from semiconducting through metallic to superconducting. In contrast, using both theory and experiment, we show here that the conductance of metal |single molecule| metal junctions involving aromatic donor moieties (dialkylterthiophene, dialkylbenzene) increase by over an order of magnitude upon formation of charge transfer (CT) complexes with tetracyanoethylene (TCNE). This enhancement occurs because CT complex formation creates a new resonance in the transmission function, close to the metal contact Fermi energy, that is a signal of room-temperature quantum interference. Electronic supplementary information (ESI) available: Synthesis of 1c; experimental details of conductance measurements, formation of charge transfer complexes of 1c and 2 in solution; further details of theoretical methods. See DOI: 10.1039/c5nr04420k

  18. Transfer of the EPA/NIH Chemical Information System (CIS) to Private Management.

    ERIC Educational Resources Information Center

    Kadec, Sarah T.; Jover, Antonio

    This paper discusses the programmatic concerns, the evaluation, and the ultimate decisions which led to the transfer of CIS (Chemical Information System) to the private sector. CIS is a complex, integrated system of some 20 chemical databases and data analysis programs which provide access to physical, toxicological, environmental effects, and…

  19. Complexity of genetic sequences modified by horizontal gene transfer and degraded-DNA uptake

    NASA Astrophysics Data System (ADS)

    Tremberger, George; Dehipawala, S.; Nguyen, A.; Cheung, E.; Sullivan, R.; Holden, T.; Lieberman, D.; Cheung, T.

    2015-09-01

    Horizontal gene transfer has been a major vehicle for efficient transfer of genetic materials among living species and could be one of the sources for noncoding DNA incorporation into a genome. Our previous study of lnc- RNA sequence complexity in terms of fractal dimension and information entropy shows a tight regulation among the studied genes in numerous diseases. The role of sequence complexity in horizontal transferred genes was investigated with Mealybug in symbiotic relation with a 139K genome microbe and Deinococcus radiodurans as examples. The fractal dimension and entropy showed correlation R-sq of 0.82 (N = 6) for the studied Deinococcus radiodurans sequences. For comparison the Deinococcus radiodurans oxidative stress tolerant catalase and superoxide dismutase genes under extracellular dGMP growth condition showed R-sq ~ 0.42 (N = 6); and the studied arsenate reductase horizontal transferred genes for toxicity survival in several microorganisms showed no correlation. Simulation results showed that R-sq < 0.4 would be improbable at less than one percent chance, suggestive of additional selection pressure when compared to the R-sq ~ 0.29 (N = 21) in the studied transferred genes in Mealybug. The mild correlation of R-sq ~ 0.5 for fractal dimension versus transcription level in the studied Deinococcus radiodurans sequences upon extracellular dGMP growth condition would suggest that lower fractal dimension with less electron density fluctuation favors higher transcription level.

  20. Production and Transfer of Energy and Information in Hamiltonian Systems

    PubMed Central

    Antonopoulos, Chris G.; Bianco-Martinez, Ezequiel; Baptista, Murilo S.

    2014-01-01

    We present novel results that relate energy and information transfer with sensitivity to initial conditions in chaotic multi-dimensional Hamiltonian systems. We show the relation among Kolmogorov-Sinai entropy, Lyapunov exponents, and upper bounds for the Mutual Information Rate calculated in the Hamiltonian phase space and on bi-dimensional subspaces. Our main result is that the net amount of transfer from kinetic to potential energy per unit of time is a power-law of the upper bound for the Mutual Information Rate between kinetic and potential energies, and also a power-law of the Kolmogorov-Sinai entropy. Therefore, transfer of energy is related with both transfer and production of information. However, the power-law nature of this relation means that a small increment of energy transferred leads to a relatively much larger increase of the information exchanged. Then, we propose an “experimental” implementation of a 1-dimensional communication channel based on a Hamiltonian system, and calculate the actual rate with which information is exchanged between the first and last particle of the channel. Finally, a relation between our results and important quantities of thermodynamics is presented. PMID:24586891

  1. Quantum ferroelectricity in charge-transfer complex crystals

    PubMed Central

    Horiuchi, Sachio; Kobayashi, Kensuke; Kumai, Reiji; Minami, Nao; Kagawa, Fumitaka; Tokura, Yoshinori

    2015-01-01

    Quantum phase transition achieved by fine tuning the continuous phase transition down to zero kelvin is a challenge for solid state science. Critical phenomena distinct from the effects of thermal fluctuations can materialize when the electronic, structural or magnetic long-range order is perturbed by quantum fluctuations between degenerate ground states. Here we have developed chemically pure tetrahalo-p-benzoquinones of n iodine and 4–n bromine substituents (QBr4–nIn, n=0–4) to search for ferroelectric charge-transfer complexes with tetrathiafulvalene (TTF). Among them, TTF–QBr2I2 exhibits a ferroelectric neutral–ionic phase transition, which is continuously controlled over a wide temperature range from near-zero kelvin to room temperature under hydrostatic pressure. Quantum critical behaviour is accompanied by a much larger permittivity than those of other neutral–ionic transition compounds, such as well-known ferroelectric complex of TTF–QCl4 and quantum antiferroelectric of dimethyl–TTF–QBr4. By contrast, TTF–QBr3I complex, another member of this compound family, shows complete suppression of the ferroelectric spin-Peierls-type phase transition. PMID:26076656

  2. Quantum ferroelectricity in charge-transfer complex crystals.

    PubMed

    Horiuchi, Sachio; Kobayashi, Kensuke; Kumai, Reiji; Minami, Nao; Kagawa, Fumitaka; Tokura, Yoshinori

    2015-01-01

    Quantum phase transition achieved by fine tuning the continuous phase transition down to zero kelvin is a challenge for solid state science. Critical phenomena distinct from the effects of thermal fluctuations can materialize when the electronic, structural or magnetic long-range order is perturbed by quantum fluctuations between degenerate ground states. Here we have developed chemically pure tetrahalo-p-benzoquinones of n iodine and 4-n bromine substituents (QBr4-nIn, n=0-4) to search for ferroelectric charge-transfer complexes with tetrathiafulvalene (TTF). Among them, TTF-QBr2I2 exhibits a ferroelectric neutral-ionic phase transition, which is continuously controlled over a wide temperature range from near-zero kelvin to room temperature under hydrostatic pressure. Quantum critical behaviour is accompanied by a much larger permittivity than those of other neutral-ionic transition compounds, such as well-known ferroelectric complex of TTF-QCl4 and quantum antiferroelectric of dimethyl-TTF-QBr4. By contrast, TTF-QBr3I complex, another member of this compound family, shows complete suppression of the ferroelectric spin-Peierls-type phase transition. PMID:26076656

  3. Information Literacy and Transfer in Schools: Implications for Teacher Librarians

    ERIC Educational Resources Information Center

    Herring, James E.; Bush, Stephanie J.

    2011-01-01

    This study focuses on the use of the New South Wales (NSW) Department of Education and Training information literacy model in a primary school as the basis for the possible establishment of a culture of transfer of information literacy skills. The study used constructivist grounded analysis to interpret data gathered from teachers and principals.…

  4. Information transfer using wearable thin electrotactile displays with microneedle electrodes

    NASA Astrophysics Data System (ADS)

    Tezuka, Mayuko; Kitamura, Norihide; Miki, Norihisa

    2016-06-01

    Tactile sensation is considered as a promising information transfer tool that can replace or compensate for sight and hearing information. In this study, we developed a sheet-type electrotactile display with microneedle electrodes. This flexible and thin display is suitable for wearable applications. It can present tactile sensation to the skin at a low voltage by penetrating the stratum corneum with microneedles. As a proof-of-concept experiment of transferring information via tactile sensation, we first tried to convey signals of two patterns using a single display. Next, we attempted to use multiple displays and experimentally investigated the spatial resolution of the tactile sensation on the forearm. Finally, 3-bit information was successfully transferred by three devices attached to the forearm.

  5. Air-ground information transfer in the National Airspace System

    NASA Technical Reports Server (NTRS)

    Lee, Alfred T.; Lozito, Sandra

    1989-01-01

    This paper reviews NASA's Aviation Safety Reporting System incident data for a two-year period in order to identify the frequency of air-ground information transfer errors and the factors associated with their occurrence. Of the more than 14,000 primary reports received during the 1985 and 1986 reporting period, one out of four reports concerned problems of information transfer between aircraft and ATC. Approximately half of these errors were associated directly or indirectly with aircraft deviations from assigned heading or altitude. The majority of incidents cited some human-system problem such as workload, cockpit distractions, etc., as the primary contributing factor. Improvements in air-ground information transfer using existing and future (e.g., data link) technology are proposed centering on the development and application of user-centered information management principles.

  6. Usefulness of relay-information-transfer for radar QPE

    NASA Astrophysics Data System (ADS)

    Kim, Jungho; Yoo, Chulsang; Lim, Sanghun; Choi, Jeongho

    2015-12-01

    This study proposes a method of relay-information-transfer for radar QPE (quantitative precipitation estimation) to overcome the limitation of the current QPE in Korea. The Z-R relationship was selected as the QPE information to be transferred. To examine the applicability of the proposed method, three different cases of relay-information-transfer were considered: (1) from the sea to inland, (2) from inland to another inland location, and (3) over a long distance. The results were: (1) Between the two parameters of the Z-R relationship, the parameter A was found to have an explanatory power of more than 70% of the Z-R relationship from one radar to the other. (2) All three cases showed that the relay-information-transfer of the parameter A was highly applicable, especially in the initial period of a storm. (3) Areal average rainfall and the root mean square error of the radar rain rate also confirmed that the relay-information-transfer method resulted in more reasonable estimates of the parameter A in the initial period of a storm. After the initial period, however, both the conventional method and the method proposed in this study were found to provide similar and reasonable estimates.

  7. Information transfer by leaky, heterogeneous, protein kinase signaling systems

    PubMed Central

    Voliotis, Margaritis; Perrett, Rebecca M.; McWilliams, Chris; McArdle, Craig A.; Bowsher, Clive G.

    2014-01-01

    Cells must sense extracellular signals and transfer the information contained about their environment reliably to make appropriate decisions. To perform these tasks, cells use signal transduction networks that are subject to various sources of noise. Here, we study the effects on information transfer of two particular types of noise: basal (leaky) network activity and cell-to-cell variability in the componentry of the network. Basal activity is the propensity for activation of the network output in the absence of the signal of interest. We show, using theoretical models of protein kinase signaling, that the combined effect of the two types of noise makes information transfer by such networks highly vulnerable to the loss of negative feedback. In an experimental study of ERK signaling by single cells with heterogeneous ERK expression levels, we verify our theoretical prediction: In the presence of basal network activity, negative feedback substantially increases information transfer to the nucleus by both preventing a near-flat average response curve and reducing sensitivity to variation in substrate expression levels. The interplay between basal network activity, heterogeneity in network componentry, and feedback is thus critical for the effectiveness of protein kinase signaling. Basal activity is widespread in signaling systems under physiological conditions, has phenotypic consequences, and is often raised in disease. Our results reveal an important role for negative feedback mechanisms in protecting the information transfer function of saturable, heterogeneous cell signaling systems from basal activity. PMID:24395805

  8. Patent information - towards simplicity or complexity?

    NASA Astrophysics Data System (ADS)

    Shenton, Written By Kathleen; Norton, Peter; Onodera, Translated By Natsuo

    Since the advent of online services, the ability to search and find chemical patent information has improved immeasurably. Recently, integration of a multitude of files (through file merging as well as cross-file/simultaneous searches), 'intelligent' interfaces and optical technology for large amounts of data seem to achieve greater simplicity and convenience in the retrieval of patent information. In spite of these progresses, there is more essential problem which increases complexity. It is a tendency to expand indefinitely the range of claim for chemical substances by a ultra-generic description of structure (overuse of optional substituents, variable divalent groups, repeating groups, etc.) and long listing of prophetic examples. Not only does this tendency worry producers and searchers of patent databases but also prevents truly worthy inventions in future.

  9. Research Strategy for Modeling the Complexities of Turbine Heat Transfer

    NASA Technical Reports Server (NTRS)

    Simoneau, Robert J.

    1996-01-01

    The subject of this paper is a NASA research program, known as the Coolant Flow Management Program, which focuses on the interaction between the internal coolant channel and the external film cooling of a turbine blade and/or vane in an aircraft gas turbine engine. The turbine gas path is really a very complex flow field. The combination of strong pressure gradients, abrupt geometry changes and intersecting surfaces, viscous forces, rotation, and unsteady blade/vane interactions all combine to offer a formidable challenge. To this, in the high pressure turbine, we add the necessity of film cooling. The ultimate goal of the turbine designer is to maintain or increase the high level of turbine performance and at the same time reduce the amount of coolant flow needed to achieve this end. Simply stated, coolant flow is a penalty on the cycle and reduces engine thermal efficiency. Accordingly, understanding the flow field and heat transfer associated with the coolant flow is a priority goal. It is important to understand both the film cooling and the internal coolant flow, particularly their interaction. Thus, the motivation for the Coolant Flow Management Program. The paper will begin with a brief discussion of the management and research strategy, will then proceed to discuss the current attack from the internal coolant side, and will conclude by looking at the film cooling effort - at all times keeping sight of the primary goal the interaction between the two. One of the themes of this paper is that complex heat transfer problems of this nature cannot be attacked by single researchers or even groups of researchers, each working alone. It truly needs the combined efforts of a well-coordinated team to make an impact. It is important to note that this is a government/industry/university team effort.

  10. Information to Change the World--Fulfilling the Information Needs of Technology Transfer.

    ERIC Educational Resources Information Center

    Duberman, Josh; Zeller, Martin

    1996-01-01

    Provides an introduction to fulfilling the information needs of technology transfer. Highlights include a definition of technology transfer; government and university involvement; industry's role; publishers; an annotated list of information sources and contacts; technology assessment, including patent searching, competitive intelligence, and…

  11. Control of the efficiency of agonist-induced information transfer and stability of the ternary complex containing the delta opioid receptor and the alpha subunit of G(i1) by mutation of a receptor/G protein contact interface.

    PubMed

    Moon, H E; Bahia, D S; Cavalli, A; Hoffmann, M; Milligan, G

    2001-09-01

    Fusion proteins were constructed between the delta opioid receptor and forms of the alpha subunit of G(i1) in which cysteine(351) was mutated to a range of amino acids. GDP reduced the binding of the agonist [(3)H]DADLE but not the antagonist [(3)H]naltrindole to both the receptor alone and all the delta opioid receptor-Cys(351)XaaG(i1)alpha fusion proteins. For the fusion proteins the pEC(50) for GDP was strongly correlated with the n-octanol/H(2)O partition co-efficient of G protein residue(351). Fusion proteins in which this residue was either isoleucine or glycine had similar observed binding kinetics for [(3)H]DADLE. However, the rate of dissociation of [(3)H]DADLE was substantially greater for the glycine-containing fusion protein than that containing isoleucine, indicating that more hydrophobic residues imbued greater stability to the agonist-receptor-G protein ternary complex. This resulted in a higher affinity of binding of [(3)H]DADLE to the fusion protein containing isoleucine(351). In expectation with the binding data, maximal DADLE-stimulated GTP hydrolysis by the isoleucine(351)-containing fusion protein was two-fold greater and the potency of DADLE seven-fold higher than for the version containing glycine. These results demonstrate that the stability of the ternary complex between delta opioid receptor, G(i1)alpha and an agonist (but not antagonist) ligand is dependent upon the nature of residue(351) of the G protein and that this determines the effectiveness of information flow from the receptor to the G protein. PMID:11522323

  12. Information transfer in auditoria and room-acoustical quality.

    PubMed

    Summers, Jason E

    2013-04-01

    It is hypothesized that room-acoustical quality correlates with the information-transfer rate. Auditoria are considered as multiple-input multiple-output communication channels and a theory of information-transfer is outlined that accounts for time-variant multipath, spatial hearing, and distributed directional sources. Source diversity and spatial hearing are shown to be the mechanisms through which multipath increases the information-transfer rate by overcoming finite spatial resolution. In addition to predictions that are confirmed by recent and historical findings, the theory provides explanations for the influence of factors such as musical repertoire and ensemble size on subjective preference and the influence of multisource, multichannel auralization on perceived realism. PMID:23556686

  13. Effect of perturbations on information transfer in spin chains

    SciTech Connect

    Ronke, R.; D'Amico, I.; Spiller, T. P.

    2011-01-15

    Spin chains have been proposed as a reliable and convenient way of transferring information and entanglement in a quantum computational context. Nonetheless, it has to be expected that any physical implementation of these systems will be subject to several perturbative factors which could potentially diminish the transfer quality. In this paper, we investigate a number of possible fabrication defects in the spin chains themselves as well as the effect of nonsynchronous or imperfect input operations, with a focus on the case of multiple excitation and qubit transfer. We consider both entangled and unentangled states and, in particular, the transfer of an entangled pair of adjacent spins at one end of a chain under the mirroring rule and also the creation of entanglement resulting from injection at both end spins.

  14. Information filtering in complex weighted networks

    NASA Astrophysics Data System (ADS)

    Radicchi, Filippo; Ramasco, José J.; Fortunato, Santo

    2011-04-01

    Many systems in nature, society, and technology can be described as networks, where the vertices are the system’s elements, and edges between vertices indicate the interactions between the corresponding elements. Edges may be weighted if the interaction strength is measurable. However, the full network information is often redundant because tools and techniques from network analysis do not work or become very inefficient if the network is too dense, and some weights may just reflect measurement errors and need to be be discarded. Moreover, since weight distributions in many complex weighted networks are broad, most of the weight is concentrated among a small fraction of all edges. It is then crucial to properly detect relevant edges. Simple thresholding would leave only the largest weights, disrupting the multiscale structure of the system, which is at the basis of the structure of complex networks and ought to be kept. In this paper we propose a weight-filtering technique based on a global null model [Global Statistical Significance (GloSS) filter], keeping both the weight distribution and the full topological structure of the network. The method correctly quantifies the statistical significance of weights assigned independently to the edges from a given distribution. Applications to real networks reveal that the GloSS filter is indeed able to identify relevant connections between vertices.

  15. Information Transfer and the Adoption of Agricultural Innovations.

    ERIC Educational Resources Information Center

    Longo, Rose Mary Juliano

    1990-01-01

    Data collected in the Federal District of Brazil were analyzed in terms of information transfer through mass media and interpersonal communication and how they influence farmers in the Federal District of Brazil in their decisions to adopt agricultural innovations. (42 references) (EAM)

  16. INFORMATION TRANSFER IN THE OFFICE OF RESEARCH AND DEVELOPMENT

    EPA Science Inventory

    The report presents the results of a study conducted to determine the effectiveness of the Office of Research and Development's (ORD) information transfer activities. The type and volume of activity is reported as well as costs, intended and actual audiences, and the method used ...

  17. Some Issues in Information Transfer: A Third World Development Perspective.

    ERIC Educational Resources Information Center

    Neelameghan, A.

    One of the many problems of developing nations is the scarcity of the information required for development planning, its concomitant abundance in more developed nations, and the lack of a truly viable infrastructure to achieve its economic transfer. Political and administrative structures must be created that are responsive to the new scales of…

  18. Information Networks: A Probablistic Model for Hierarchical Message Transfer.

    ERIC Educational Resources Information Center

    Bhat, U. Narayan; And Others

    A strictly hierarchical message transfer scheme requires that a message follow a specified referral path unless finally it is either rejected or filled at any one of the information centers of the network. Thus at each node in the network three decisions can be made: satisfy, reject or refer the message to the succeeding node in the hierarchy.…

  19. The electronic transfer of information and aerospace knowledge diffusion

    NASA Technical Reports Server (NTRS)

    Pinelli, Thomas E.; Bishop, Ann P.; Barclay, Rebecca O.; Kennedy, John M.

    1992-01-01

    Increasing reliance on and investment in information technology and electronic networking systems presupposes that computing and information technology will play a motor role in the diffusion of aerospace knowledge. Little is known, however, about actual information technology needs, uses, and problems within the aerospace knowledge diffusion process. The authors state that the potential contributions of information technology to increased productivity and competitiveness will be diminished unless empirically derived knowledge regarding the information-seeking behavior of the members of the social system - those who are producing, transferring, and using scientific and technical information - is incorporated into a new technology policy framework. Research into the use of information technology and electronic networks by U.S. aerospace engineers and scientists, collected as part of a research project designed to study aerospace knowledge diffusion, is presented in support of this assertion.

  20. Measuring information transfer in a soft robotic arm.

    PubMed

    Nakajima, K; Schmidt, N; Pfeifer, R

    2015-06-01

    Soft robots can exhibit diverse behaviors with simple types of actuation by partially outsourcing control to the morphological and material properties of their soft bodies, which is made possible by the tight coupling between control, body, and environment. In this paper, we present a method that will quantitatively characterize these diverse spatiotemporal dynamics of a soft body based on the information-theoretic approach. In particular, soft bodies have the ability to propagate the effect of actuation through the entire body, with a certain time delay, due to their elasticity. Our goal is to capture this delayed interaction in a quantitative manner based on a measure called momentary information transfer. We extend this measure to soft robotic applications and demonstrate its power using a physical soft robotic platform inspired by the octopus. Our approach is illustrated in two ways. First, we statistically characterize the delayed actuation propagation through the body as a strength of information transfer. Second, we capture this information propagation directly as local information dynamics. As a result, we show that our approach can successfully characterize the spatiotemporal dynamics of the soft robotic platform, explicitly visualizing how information transfers through the entire body with delays. Further extension scenarios of our approach are discussed for soft robotic applications in general. PMID:25970447

  1. Coherent Control Protocol for Separating Energy-Transfer Pathways in Photosynthetic Complexes by Chiral Multidimensional Signals†

    PubMed Central

    Abramavicius, Darius; Mukamel, Shaul

    2013-01-01

    Adaptive optimizations performed using a genetic algorithm are employed to construct optimal laser pulse configurations that separate spectroscopic features associated with the two main energy-transfer pathways in the third-order nonlinear optical response simulated for the Fenna–Matthews–Olson (FMO) photosynthetic complex from the green sulfur bacterium Chlorobium tepidum. Superpositions of chirality-induced tensor components in both collinear and noncollinear pulse configurations are analyzed. The optimal signals obtained by manipulating the ratios of various 2D spectral peaks reveal detailed information about the excitation dynamics. PMID:21495702

  2. Scalable quantum information transfer between nitrogen-vacancy-center ensembles

    SciTech Connect

    Zhang, Feng-yang; Yang, Chui-Ping; Song, He-Shan

    2015-04-15

    We propose an architecture for realizing quantum information transfer (QIT). In this architecture, a LC circuit is used to induce the necessary interaction between flux qubits, each magnetically coupling to a nitrogen-vacancy center ensemble (NVCE). We explicitly show that for resonant interaction and large detuning cases, high-fidelity QIT between two spatially-separated NVCEs can be implemented. Our proposal can be extended to achieve QIT between any two selected NVCEs in a large hybrid system by adjusting system parameters, which is important in large scale quantum information processing. - Highlights: • Quantum information transfer between any two selected NV ensembles is implemented. • This architecture is robust against the dissipation of the system. • We explicitly show that for resonant interaction and large detuning cases.

  3. Conceptual model for transferring information between small watersheds

    USGS Publications Warehouse

    Cleaves, E.T.

    2003-01-01

    Stream and watershed management and restoration can be greatly facilitated through use of physiographic landform classification to organize and communicate natural resource, hazard, and environmental information at a broad scale (1:250,000) as illustrated by the Piedmont and Coastal Plain Provinces in Maryland, or at a small scale (1:24,000) as illustrated using divisions and zones combined with a conceptual model. The conceptual model brings together geology, surficial processes, landforms and land use change information at the small watershed scale and facilitates transfer of information from one small watershed to another with similar geology and landforms. Stream flow, sediment erosion, and water quality illustrate the use of the model.

  4. Serotonergic Psychedelics Temporarily Modify Information Transfer in Humans

    PubMed Central

    Alonso, Joan Francesc; Romero, Sergio; Mañanas, Miquel Àngel

    2015-01-01

    Background: Psychedelics induce intense modifications in the sensorium, the sense of “self,” and the experience of reality. Despite advances in our understanding of the molecular and cellular level mechanisms of these drugs, knowledge of their actions on global brain dynamics is still incomplete. Recent imaging studies have found changes in functional coupling between frontal and parietal brain structures, suggesting a modification in information flow between brain regions during acute effects. Methods: Here we assessed the psychedelic-induced changes in directionality of information flow during the acute effects of a psychedelic in humans. We measured modifications in connectivity of brain oscillations using transfer entropy, a nonlinear measure of directed functional connectivity based on information theory. Ten healthy male volunteers with prior experience with psychedelics participated in 2 experimental sessions. They received a placebo or a dose of ayahuasca, a psychedelic preparation containing the serotonergic 5-HT2A agonist N,N-dimethyltryptamine. Results: The analysis showed significant changes in the coupling of brain oscillations between anterior and posterior recording sites. Transfer entropy analysis showed that frontal sources decreased their influence over central, parietal, and occipital sites. Conversely, sources in posterior locations increased their influence over signals measured at anterior locations. Exploratory correlations found that anterior-to-posterior transfer entropy decreases were correlated with the intensity of subjective effects, while the imbalance between anterior-to-posterior and posterior-to-anterior transfer entropy correlated with the degree of incapacitation experienced. Conclusions: These results suggest that psychedelics induce a temporary disruption of neural hierarchies by reducing top-down control and increasing bottom-up information transfer in the human brain. PMID:25820842

  5. Rényi’s information transfer between financial time series

    NASA Astrophysics Data System (ADS)

    Jizba, Petr; Kleinert, Hagen; Shefaat, Mohammad

    2012-05-01

    In this paper, we quantify the statistical coherence between financial time series by means of the Rényi entropy. With the help of Campbell’s coding theorem, we show that the Rényi entropy selectively emphasizes only certain sectors of the underlying empirical distribution while strongly suppressing others. This accentuation is controlled with Rényi’s parameter q. To tackle the issue of the information flow between time series, we formulate the concept of Rényi’s transfer entropy as a measure of information that is transferred only between certain parts of underlying distributions. This is particularly pertinent in financial time series, where the knowledge of marginal events such as spikes or sudden jumps is of a crucial importance. We apply the Rényian information flow to stock market time series from 11 world stock indices as sampled at a daily rate in the time period 02.01.1990-31.12.2009. Corresponding heat maps and net information flows are represented graphically. A detailed discussion of the transfer entropy between the DAX and S&P500 indices based on minute tick data gathered in the period 02.04.2008-11.09.2009 is also provided. Our analysis shows that the bivariate information flow between world markets is strongly asymmetric with a distinct information surplus flowing from the Asia-Pacific region to both European and US markets. An important yet less dramatic excess of information also flows from Europe to the US. This is particularly clearly seen from a careful analysis of Rényi information flow between the DAX and S&P500 indices.

  6. Intramolecular energy transfer reactions in polymetallic complexes.. Progress report, 1991--1992

    SciTech Connect

    Petersen, J.

    1992-12-01

    (1) Excited-state energy transfer: The major effort was an attempt to sensitize the photoelimination of H{sub 2} from a bimetallic, metal-dihydride complex. These complexes have involved Fe, Ru, and Co complexes. (2) Excited-state electron transfer (charge separation): A series of diad and triad complexes were prepared in order to sustain charge separation in an artificial photosynthetic system.

  7. Solvation-Driven Charge Transfer and Localization in Metal Complexes

    PubMed Central

    2016-01-01

    Conspectus In any physicochemical process in liquids, the dynamical response of the solvent to the solutes out of equilibrium plays a crucial role in the rates and products: the solvent molecules react to the changes in volume and electron density of the solutes to minimize the free energy of the solution, thus modulating the activation barriers and stabilizing (or destabilizing) intermediate states. In charge transfer (CT) processes in polar solvents, the response of the solvent always assists the formation of charge separation states by stabilizing the energy of the localized charges. A deep understanding of the solvation mechanisms and time scales is therefore essential for a correct description of any photochemical process in dense phase and for designing molecular devices based on photosensitizers with CT excited states. In the last two decades, with the advent of ultrafast time-resolved spectroscopies, microscopic models describing the relevant case of polar solvation (where both the solvent and the solute molecules have a permanent electric dipole and the mutual interaction is mainly dipole–dipole) have dramatically progressed. Regardless of the details of each model, they all assume that the effect of the electrostatic fields of the solvent molecules on the internal electronic dynamics of the solute are perturbative and that the solvent–solute coupling is mainly an electrostatic interaction between the constant permanent dipoles of the solute and the solvent molecules. This well-established picture has proven to quantitatively rationalize spectroscopic effects of environmental and electric dynamics (time-resolved Stokes shifts, inhomogeneous broadening, etc.). However, recent computational and experimental studies, including ours, have shown that further improvement is required. Indeed, in the last years we investigated several molecular complexes exhibiting photoexcited CT states, and we found that the current description of the formation and

  8. The complexities of DNA transfer during a social setting.

    PubMed

    Goray, Mariya; van Oorschot, Roland A H

    2015-03-01

    When questions relating to how a touch DNA sample from a specific individual got to where it was sampled from, one has limited data available to provide an assessment on the likelihood of specific transfer events within a proposed scenario. This data is mainly related to the impact of some key variables affecting transfer that are derived from structured experiments. Here we consider the effects of unstructured social interactions on the transfer of touch DNA. Unscripted social exchanges of three individuals having a drink together while sitting at a table were video recorded and DNA samples were collected and profiled from all relevant items touched during each sitting. Attempts were made to analyze when and how DNA was transferred from one object to another. The analyses demonstrate that simple minor everyday interactions involving only a few items in some instances lead to detectable DNA being transferred among individuals and objects without them having contacted each other through secondary and further transfer. Transfer was also observed to be bi-directional. Furthermore, DNA of unknown source on hands or objects can be transferred and interfere with the interpretation of profiles generated from targeted touched surfaces. This study provides further insight into the transfer of DNA that may be useful when considering the likelihood of alternate scenarios of how a DNA sample got to where it was found. PMID:25454534

  9. Teacher Modeling Using Complex Informational Texts

    ERIC Educational Resources Information Center

    Fisher, Douglas; Frey, Nancy

    2015-01-01

    Modeling in complex texts requires that teachers analyze the text for factors of qualitative complexity and then design lessons that introduce students to that complexity. In addition, teachers can model the disciplinary nature of content area texts as well as word solving and comprehension strategies. Included is a planning guide for think aloud.

  10. Quantifying and transferring contextual information in object detection.

    PubMed

    Zheng, Wei-Shi; Gong, Shaogang; Xiang, Tao

    2012-04-01

    Context is critical for reducing the uncertainty in object detection. However, context modeling is challenging because there are often many different types of contextual information coexisting with different degrees of relevance to the detection of target object(s) in different images. It is therefore crucial to devise a context model to automatically quantify and select the most effective contextual information for assisting in detecting the target object. Nevertheless, the diversity of contextual information means that learning a robust context model requires a larger training set than learning the target object appearance model, which may not be available in practice. In this work, a novel context modeling framework is proposed without the need for any prior scene segmentation or context annotation. We formulate a polar geometric context descriptor for representing multiple types of contextual information. In order to quantify context, we propose a new maximum margin context (MMC) model to evaluate and measure the usefulness of contextual information directly and explicitly through a discriminant context inference method. Furthermore, to address the problem of context learning with limited data, we exploit the idea of transfer learning based on the observation that although two categories of objects can have very different visual appearance, there can be similarity in their context and/or the way contextual information helps to distinguish target objects from nontarget objects. To that end, two novel context transfer learning models are proposed which utilize training samples from source object classes to improve the learning of the context model for a target object class based on a joint maximum margin learning framework. Experiments are carried out on PASCAL VOC2005 and VOC2007 data sets, a luggage detection data set extracted from the i-LIDS data set, and a vehicle detection data set extracted from outdoor surveillance footage. Our results validate the

  11. 76 FR 35219 - Federal Acquisition Regulation; Information Collection; Payment by Electronic Fund Transfer

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-06-16

    ... contract by electronic fund transfer (EFT). The information necessary to make the EFT transaction is... Regulation; Information Collection; Payment by Electronic Fund Transfer AGENCY: Department of Defense (DOD... extension of a previously approved information collection requirement concerning payment by electronic...

  12. Tech transfer outreach. An informal proceedings of the first technology transfer/communications conference

    SciTech Connect

    Liebetrau, S.

    1992-10-01

    This document provides an informal summary of the conference workshop sessions. ``Tech Transfer Outreach!`` was originally designed as an opportunity for national laboratory communications and technology transfer staff to become better acquainted and to discuss matters of mutual interest. When DOE field office personnel asked if they could attend, and then when one of our keynote speakers became a participant in the discussions, the actual event grew in importance. The conference participants--the laboratories and DOE representatives from across the nation--worked to brainstorm ideas. Their objective: identify ways to cooperate for effective (and cost-effective) technology transfer outreach. Thus, this proceedings is truly a product of ten national laboratories and DOE, working together. It candidly presents the discussion of issues and the ideas generated by each working group. The issues and recommendations are a consensus of their views.

  13. Information transfer satellite concept study. Volume 2: Technical

    NASA Technical Reports Server (NTRS)

    Bergin, P.; Kincade, C.; Kurpiewski, D.; Leinhaupel, F.; Millican, F.; Onstad, R.

    1971-01-01

    The ITS concept study is preceded by two requirements studies whose primary objectives are to identify viable demands and to develop the functional requirements associated with these demands. In addition to continuing this basic activity the ITS concept study objectives are to: (1) develop tools and techniques for planning advanced information transfer satellite communications systems, and to (2) select viable systems for further analysis both in their near-term and in the far-term aspects.

  14. Is there an optimal basis to maximise optical information transfer?

    NASA Astrophysics Data System (ADS)

    Chen, Mingzhou; Dholakia, Kishan; Mazilu, Michael

    2016-03-01

    We establish the concept of the density of the optical degrees of freedom that may be applied to any photonics based system. As a key example of this versatile approach we explore information transfer using optical communication. We demonstrate both experimentally, theoretically and numerically that the use of a basis set with fields containing optical vortices does not increase the telecommunication capacity of an optical system.

  15. Is there an optimal basis to maximise optical information transfer?

    PubMed Central

    Chen, Mingzhou; Dholakia, Kishan; Mazilu, Michael

    2016-01-01

    We establish the concept of the density of the optical degrees of freedom that may be applied to any photonics based system. As a key example of this versatile approach we explore information transfer using optical communication. We demonstrate both experimentally, theoretically and numerically that the use of a basis set with fields containing optical vortices does not increase the telecommunication capacity of an optical system. PMID:26976626

  16. Transferability and data access issues. [decision information display system

    NASA Technical Reports Server (NTRS)

    Ferreros, A. V.

    1981-01-01

    The evolution and current operational mode of the domestic information display system (DIDS) now known as the decision information display system are described. This minicomputer based system, developed from a NASA-generated image processing system, was designed to display federal statistical data for a variety of geographic areas in the form of choropleth maps. The application of DIDS in South Carolina is discussed as well as the progress made and issues that emerged in using the data base on a state and county level. The hardware base for the system, how this user friendly system works, and the possibility of transferring data to remote systems are examined.

  17. Hydrogenase/ferredoxin charge-transfer complexes: effect of hydrogenase mutations on the complex association.

    PubMed

    Long, Hai; King, Paul W; Ghirardi, Maria L; Kim, Kwiseon

    2009-04-23

    The [FeFe]-hydrogenases in the green alga Chlamydomonas reinhardtii utilize photogenerated electrons to reduce protons into hydrogen gas. The electrons are supplied from photosystem I and transferred to the [FeFe]-hydrogenase through specific hydrogenase-ferredoxin association. To understand how structural and kinetic factors control the association better, we used Brownian dynamics simulation methods to simulate the charge-transfer complex formation between both native and in silico mutants of the [FeFe]-hydrogenase HYDA2 and the [2Fe2S]-ferredoxin FDX1 from C. reinhardtii . The changes in binding free energy between different HYDA2 mutants and the native FDX1 were calculated by the free-energy perturbation method. Within the limits of our current models, we found that two HYDA2 mutations, T99K(H) and D102K(H), led to lower binding free energies and higher association rate with FDX1 and are thus promising targets for improving hydrogen production rates in engineered organisms. PMID:19317477

  18. Renyi complexities and information planes: Atomic structure in conjugated spaces

    NASA Astrophysics Data System (ADS)

    Antolín, J.; López-Rosa, S.; Angulo, J. C.

    2009-05-01

    Generalized Renyi complexity measures are defined and numerically analyzed for atomic one-particle densities in both conjugated spaces. These complexities provide, as particular cases, the previously known statistical and Fisher-Shannon complexities. The generalized complexities provide information on the atomic shell structure and shell-filling patterns, allowing to appropriately weight different regions of the electronic cloud.

  19. Using social media to facilitate knowledge transfer in complex engineering environments: a primer for educators

    NASA Astrophysics Data System (ADS)

    Murphy, Glen; Salomone, Sonia

    2013-03-01

    While highly cohesive groups are potentially advantageous they are also often correlated with the emergence of knowledge and information silos based around those same functional or occupational clusters. Consequently, an essential challenge for engineering organisations wishing to overcome informational silos is to implement mechanisms that facilitate, encourage and sustain interactions between otherwise disconnected groups. This paper acts as a primer for those seeking to gain an understanding of the design, functionality and utility of a suite of software tools generically termed social media technologies in the context of optimising the management of tacit engineering knowledge. Underpinned by knowledge management theory and using detailed case examples, this paper explores how social media technologies achieve such goals, allowing for the transfer of knowledge by tapping into the tacit and explicit knowledge of disparate groups in complex engineering environments.

  20. Mitochondrial electron transfer chain complexes inhibition by different organochalcogens.

    PubMed

    Puntel, Robson L; Roos, Daniel H; Seeger, Rodrigo Lopes; Rocha, João B T

    2013-02-01

    Mitochondrial dysfunction plays a pivotal role in the cell toxicology and death decision. The aim of the present study was to investigate the effect of three organocompounds (ebselen [Ebs], diphenyl diselenide [(PhSe)(2)] and diphenyl ditelluride [(PhTe)(2)]) on mitochondrial complexes (I, II, I-III, II-III and IV) activity from rat liver and kidney to determine their potential role as molecular targets of organochalcogens. All studied organochalcogens caused a statistically significant inhibition of the mitochondrial complex I activity. Ebs and (PhTe)(2) caused a statistically significant inhibition of the mitochondrial complex II activity in both hepatic and renal membranes. Hepatic mitochondrial complex II activity was practically unchanged by (PhSe)(2), whereas it significantly inhibited renal complex II activity. Mitochondrial complex IV activity was practically unchanged by the organochalcogens. Furthermore, organochalcogens inhibited the mitochondrial respiration supported by complex I or complex II substrates. The inhibitory effect of Ebs, (PhSe)(2) and (PhTe)(2) on mitochondrial complex I was prevented by NADH, but it was not prevented by catalase (CAT) and/or superoxide dismutase (SOD). Additionally, the organochalcogens-induced inhibition of complex I and II was completely reversed by reduced glutathione (GSH). In conclusion, Ebs, (PhSe)(2) and (PhTe)(2) were more effective inhibitors of renal and hepatic mitochondrial complex I than complex II, whereas complexes III and IV were little modified by these compounds. Taking into account the presented results, we suggest that organochalcogen-induced mitochondrial complexes I and II inhibition can be mediated by their thiol oxidation activity, i.e., Ebs, (PhSe)(2) and (PhTe)(2) can oxidize critical thiol groups from mitochondrial complexes I and II. So, mitochondrial dysfunction can be considered an important factor in the toxicity of Ebs, (PhSe)(2) and (PhTe)(2). PMID:23103426

  1. Nonlocal Quantum Information Transfer Without Superluminal Signalling and Communication

    NASA Astrophysics Data System (ADS)

    Walleczek, Jan; Grössing, Gerhard

    2016-01-01

    It is a frequent assumption that—via superluminal information transfers—superluminal signals capable of enabling communication are necessarily exchanged in any quantum theory that posits hidden superluminal influences. However, does the presence of hidden superluminal influences automatically imply superluminal signalling and communication? The non-signalling theorem mediates the apparent conflict between quantum mechanics and the theory of special relativity. However, as a `no-go' theorem there exist two opposing interpretations of the non-signalling constraint: foundational and operational. Concerning Bell's theorem, we argue that Bell employed both interpretations, and that he finally adopted the operational position which is associated often with ontological quantum theory, e.g., de Broglie-Bohm theory. This position we refer to as "effective non-signalling". By contrast, associated with orthodox quantum mechanics is the foundational position referred to here as "axiomatic non-signalling". In search of a decisive communication-theoretic criterion for differentiating between "axiomatic" and "effective" non-signalling, we employ the operational framework offered by Shannon's mathematical theory of communication, whereby we distinguish between Shannon signals and non-Shannon signals. We find that an effective non-signalling theorem represents two sub-theorems: (1) Non-transfer-control (NTC) theorem, and (2) Non-signification-control (NSC) theorem. Employing NTC and NSC theorems, we report that effective, instead of axiomatic, non-signalling is entirely sufficient for prohibiting nonlocal communication. Effective non-signalling prevents the instantaneous, i.e., superluminal, transfer of message-encoded information through the controlled use—by a sender-receiver pair —of informationally-correlated detection events, e.g., in EPR-type experiments. An effective non-signalling theorem allows for nonlocal quantum information transfer yet—at the same time

  2. Identifying changes in EEG information transfer during drowsy driving by transfer entropy.

    PubMed

    Huang, Chih-Sheng; Pal, Nikhil R; Chuang, Chun-Hsiang; Lin, Chin-Teng

    2015-01-01

    Drowsy driving is a major cause of automobile accidents. Previous studies used neuroimaging based approaches such as analysis of electroencephalogram (EEG) activities to understand the brain dynamics of different cortical regions during drowsy driving. However, the coupling between brain regions responding to this vigilance change is still unclear. To have a comprehensive understanding of neural mechanisms underlying drowsy driving, in this study we use transfer entropy, a model-free measure of effective connectivity based on information theory. We investigate the pattern of information transfer between brain regions when the vigilance level, which is derived from the driving performance, changes from alertness to drowsiness. Results show that the couplings between pairs of frontal, central, and parietal areas increased at the intermediate level of vigilance, which suggests that an enhancement of the cortico-cortical interaction is necessary to maintain the task performance and prevent behavioral lapses. Additionally, the occipital-related connectivity magnitudes monotonically decreases as the vigilance level declines, which further supports the cortical gating of sensory stimuli during drowsiness. Neurophysiological evidence of mutual relationships between brain regions measured by transfer entropy might enhance the understanding of cortico-cortical communication during drowsy driving. PMID:26557069

  3. Identifying changes in EEG information transfer during drowsy driving by transfer entropy

    PubMed Central

    Huang, Chih-Sheng; Pal, Nikhil R.; Chuang, Chun-Hsiang; Lin, Chin-Teng

    2015-01-01

    Drowsy driving is a major cause of automobile accidents. Previous studies used neuroimaging based approaches such as analysis of electroencephalogram (EEG) activities to understand the brain dynamics of different cortical regions during drowsy driving. However, the coupling between brain regions responding to this vigilance change is still unclear. To have a comprehensive understanding of neural mechanisms underlying drowsy driving, in this study we use transfer entropy, a model-free measure of effective connectivity based on information theory. We investigate the pattern of information transfer between brain regions when the vigilance level, which is derived from the driving performance, changes from alertness to drowsiness. Results show that the couplings between pairs of frontal, central, and parietal areas increased at the intermediate level of vigilance, which suggests that an enhancement of the cortico-cortical interaction is necessary to maintain the task performance and prevent behavioral lapses. Additionally, the occipital-related connectivity magnitudes monotonically decreases as the vigilance level declines, which further supports the cortical gating of sensory stimuli during drowsiness. Neurophysiological evidence of mutual relationships between brain regions measured by transfer entropy might enhance the understanding of cortico-cortical communication during drowsy driving. PMID:26557069

  4. Price-Based Information Routing in Complex Satellite Networks for

    NASA Astrophysics Data System (ADS)

    Hussein, I.; Su, J.; Wang, Y.; Wyglinski, A.

    Future space-based situational awareness and space surveillance systems are envisioned to include a large array of satellites that seek to cooperatively achieve full awareness over given space and terrestrial domains. Given the complexity of the communication network architecture of such a system, in this paper we build on the system architecture that was proposed by the presenting author in the 2008 AMOS conference and propose an efficient, adaptable and scalable price-based routing and bandwidth allocation algorithm for the generation, routing and delivery of surveillance information in distributed wireless satellite networks. Due to the potentially large deployments of these satellites, the access points employed in a centralized network control scheme would easily be overwhelmed due to lack of spectral bandwidth, synchronization issues, and multiple access coordination. Alternatively, decentralized schemes could facilitate the flow and transference of information between data gatherers and data collectors via mechanisms such as (multi-hop) routing, allocation of spectral bandwidths per relaying node, and coordination between adjacent nodes. Although there are numerous techniques and concepts focusing on the network operations, control, and management of sensor networks, existing solution approaches require the use of information for routing, allocation, and decision-making that may not be readily available to the satellites in a timely fashion. This is especially true in the literature on price-based routing, where the approach is almost always game theoretic or relies on optimization techniques. Instead of seeking such techniques, in this paper we present algorithms that will (1) be energy-aware, (2) be highly adaptable and responsive to demands and seek delivery of information to desired nodes despite the fact that the source and destination are not globally known, (3) be secure, (4) be efficient in allocating bandwidth, (5) be decentralized and allow for

  5. Preparation and characterization of DABCO δ+x-C δ-60( y) charge transfer complex

    NASA Astrophysics Data System (ADS)

    Priyadarsini, K. I.; Mohan, H.; Tyagi, A. K.; Mittal, J. P.

    1994-12-01

    A stable complex of C 60 with an organic donor (tertiary amine, DABCO) has been prepared in the solid state at room temperature. The charge transfer complex, DABCO δ+x-C δ-60( y) is characterised by powder X-ray diffraction and FTIR methods. The complex is soluble in an aqueous medium and shows weak paramagnetic properties.

  6. Sequential Energy and Electron Transfer in Polynuclear Complex Sensitized TiO2 Nanoparticles.

    PubMed

    Verma, Sandeep; Kar, Prasenjit; Banerjee, Tanmay; Das, Amitava; Ghosh, Hirendra N

    2012-06-01

    Polynuclear-polypyridyl complexes exhibit a directional energy-transfer property that can improve their photosensitization activity. In the present work, the energy-transfer process is explored in a trinuclear Ru2(∧)Os1 complex using transient absorption spectroscopy. This study reveals an efficient excitation energy transfer from the terminal (Ru(II) complex) to the core (Os(II) complex) region in the ultrafast time domain (400 fs-40 ps). The excitation energy funnel is useful in improving the functionalized core activity. This is evidenced in an interfacial electron-transfer study of Ru2(∧)Os1, Ru2(∧)Ru1, and Os1 complex sensitized TiO2 nanoparticle (TiO2 NP) systems. The intramolecular energy transfer causes sequential excitation of the core part of the Ru2(∧)Os1 complex, which leads to multiexponential electron injection into TiO2 NP. Besides this, the electronic coupling between the metal ion centers stabilizes the positive charge within the trinuclear complex, which results in a slow charge recombination reaction. This study shows that polynuclear complexes can be very useful for their panchromatic effects, unidirectional energy- and electron-transfer properties. PMID:26285635

  7. Spectrophotometric study of the charge transfer complex between 2-amino-4-picoline with chloranilic acid

    NASA Astrophysics Data System (ADS)

    Alghanmi, Reem M.; Al-Attas, Amirah S.; Habeeb, Moustafa M.

    2013-02-01

    Charge transfer complex formation between 2-amino-4-picoline (2A4P) as the electron donor with chloranilic acid (CLA) as the electron acceptor has been studied spectrophotometrically in different polar solvents included acetone (AcN), ethanol (EtOH) and acetonitrile (AN). The molecular composition of the formed complex was recognized utilizing Job's, photometric and conductometric titration methods to be 1:1. The formation constants and molecular extinction coefficients were estimated using Benesi-Hildebrand equation; they recorded high values confirming high stability of the formed complex. Moreover, the results showed that the complex is more stable in acetone with lower electric permittivity compared with ethanol or acetonitrile of higher ones. The values of some spectroscopic physical parameters like oscillator strength f, transition dipole moment μ, resonance energy RN, charge transfer energy ECT, dissociation energy W, ionization potential IP and standard free energy ΔGo were determined and evaluated. The solid complex was isolated and its molecular composition was determined by elemental analysis to be 1:1. Furthermore, the solid complex was characterized using FTIR and 1H NMR measurements. They confirmed the presence of proton transfer beside charge transfer in the obtained complex. Molecular orbital calculations utilizing GAMESS computations were carried out to predict infrared spectra. They also confirmed the presence of proton transfer beside charge transfer in the formed complex.

  8. Quantifying networks complexity from information geometry viewpoint

    SciTech Connect

    Felice, Domenico Mancini, Stefano; Pettini, Marco

    2014-04-15

    We consider a Gaussian statistical model whose parameter space is given by the variances of random variables. Underlying this model we identify networks by interpreting random variables as sitting on vertices and their correlations as weighted edges among vertices. We then associate to the parameter space a statistical manifold endowed with a Riemannian metric structure (that of Fisher-Rao). Going on, in analogy with the microcanonical definition of entropy in Statistical Mechanics, we introduce an entropic measure of networks complexity. We prove that it is invariant under networks isomorphism. Above all, considering networks as simplicial complexes, we evaluate this entropy on simplexes and find that it monotonically increases with their dimension.

  9. Can complexity science inform physician leadership development?

    PubMed

    Grady, Colleen Marie

    2016-07-01

    Purpose The purpose of this paper is to describe research that examined physician leadership development using complexity science principles. Design/methodology/approach Intensive interviewing of 21 participants and document review provided data regarding physician leadership development in health-care organizations using five principles of complexity science (connectivity, interdependence, feedback, exploration-of-the-space-of-possibilities and co-evolution), which were grouped in three areas of inquiry (relationships between agents, patterns of behaviour and enabling functions). Findings Physician leaders are viewed as critical in the transformation of healthcare and in improving patient outcomes, and yet significant challenges exist that limit their development. Leadership in health care continues to be associated with traditional, linear models, which are incongruent with the behaviour of a complex system, such as health care. Physician leadership development remains a low priority for most health-care organizations, although physicians admit to being limited in their capacity to lead. This research was based on five principles of complexity science and used grounded theory methodology to understand how the behaviours of a complex system can provide data regarding leadership development for physicians. The study demonstrated that there is a strong association between physician leadership and patient outcomes and that organizations play a primary role in supporting the development of physician leaders. Findings indicate that a physician's relationship with their patient and their capacity for innovation can be extended as catalytic behaviours in a complex system. The findings also identified limiting factors that impact physicians who choose to lead, such as reimbursement models that do not place value on leadership and medical education that provides minimal opportunity for leadership skill development. Practical Implications This research provides practical

  10. Operational test report for 2706-T complex liquid transfer system

    SciTech Connect

    BENZEL, H.R.

    1999-09-01

    This document is the Operational Test Report (OTR). It enters the Record Copy of the W-259 Operational Test Procedure (HNF-3610) into the document retrieval system. Additionally, the OTR summarizes significant issues associated with testing the 2706-T waste liquid transfer and storage system.

  11. Information transfer satellite concept study. Volume 1: Summary

    NASA Technical Reports Server (NTRS)

    Bergin, P.; Kincade, C.; Kurpiewski, D.; Leinhaupel, F.; Millican, F.; Onstad, R.

    1971-01-01

    A wide range of information transfer demands were identified and analyzed. They were then combined into an appropriate set of requirements for satellite communication services. In this process the demands were ranked and combined into single and multipurpose satellite systems. A detailed analysis was performed on each satellite system to determine: total system cost, including both ground and space segments; sensitivities of the systems to various system tradeoffs; and forcing functions which control the system variations. A listing of candidate missions for detailed study is presented, along with a description of the conceptual system design and an identification of the technology developments required to bring these systems to fruition.

  12. Controls, Displays, and Information Transfer for General Aviation IFR Operations

    NASA Technical Reports Server (NTRS)

    Bergeron, H. P. (Editor); Shaughnessy, J. D. (Editor)

    1983-01-01

    The purpose of the workshop was to review and evaluate the work performed under the NASA Single Pilot IFR (SPIFR) program, to highlight and disseminate major research findings, and to provide a forum for industry, universities, and government to interact and discuss the future thrust of research in the SPIFR program. The presentations selected represent key elements of the SPIFR program. These elements are classified into five disciplinary areas: program definition, controls, displays, information transfer, and research simulation facilities. Emphasis is also placed on aircraft accident investigation.

  13. Counterfactual quantum-information transfer without transmitting any physical particles.

    PubMed

    Guo, Qi; Cheng, Liu-Yong; Chen, Li; Wang, Hong-Fu; Zhang, Shou

    2015-01-01

    We demonstrate quantum information can be transferred between two distant participants without any physical particles traveling between them. The key procedure of the counterfactual scheme is to entangle two nonlocal qubits with each other without interaction, so the scheme can also be used to generate nonlocal entanglement counterfactually. We here illustrate the scheme by using flying photon qubits and Rydberg atom qubits assisted by a mesoscopic atomic ensemble. Unlike the typical teleportation, the present scheme can transport an unknown qubit in a nondeterministic manner without prior entanglement sharing or classical communication between the two distant participants. PMID:25672936

  14. Charge-transfer complex versus σ-complex formed between TiO2 and bis(dicyanomethylene) electron acceptors.

    PubMed

    Fujisawa, Jun-ichi; Nagata, Morio; Hanaya, Minoru

    2015-11-01

    A novel group of organic-inorganic hybrid materials is created by the combination of titanium dioxide (TiO2) nanoparticles with bis(dicyanomethylene) (TCNX) electron acceptors. The TiO2-TCNX complex is produced by the nucleophilic addition reaction between a hydroxy group on the TiO2 surface and TCNX, with the formation of a σ-bond between them. The nucleophilic addition reaction generates a negatively-charged diamagnetic TCNX adsorbate that serves as an electron donor. The σ-bonded complex characteristically shows visible-light absorption due to interfacial charge-transfer (ICT) transitions. In this paper, we report on another kind of complex formation between TiO2 and TCNX. We have systematically studied the structures and visible-light absorption properties of the TiO2-TCNX complexes, with changing the electron affinity of TCNX. We found that TCNX acceptors with lower electron affinities form charge-transfer complexes with TiO2 without the σ-bond formation. The charge-transfer complexes show strong visible-light absorption due to interfacial electronic transitions with little charge-transfer nature, which are different from the ICT transitions in the σ-bond complexes. The charge-transfer complexes induce efficient light-to-current conversions due to the interfacial electronic transitions, revealing the high potential for applications to light-energy conversions. Furthermore, we demonstrate that the formation of the two kinds of complexes is selectively controlled by the electron affinity of TCNX. PMID:26418266

  15. Charge transfer complexes of N-substituted 2-pyrrolidinones

    NASA Astrophysics Data System (ADS)

    Ruostesuo, P.; Peltola, K.; Salminen, U.; Häkkinen, A.-M.

    The complex formation of 1-ethyl-2-pyrrolidinone, 1-benzyl-2-pyrrolidinone and 1-phenyl-2-pyrrolidinone with iodine, iodine monobromide and iodine monochloride has been studied by u.v. and visible spectroscopic methods in carbon tetrachloride, dichloromethane, 1,2-dichloroethane, n-heptane and cyclohexane. The results show the equilibrium constants ( K), complexation enthalpies (Δ H) and the wavelengths of maximum absorption bands (λ max) of the complexes to vary markedly with the solvent. The decrease in the K values with increasing acceptor number (AN) of the solvent may be due to the competition of the solvent and the halogen molecule for the amide; for halogenated hydrocarbon solvents can act as weak electron acceptors. The complex formation ability of the electron donors decreases in the order 1-ethyl-2-pyrrolidinone ≫ 1-benzyl-2-pyrrolidinone ≫ 1-phenyl-2-pyrrolidinone, and the electron acceptor properties decrease in the order iodine monochloride ≫ iodine monobromide ≫ iodine.

  16. Cross-modal transfer of statistical information benefits from sleep.

    PubMed

    Durrant, Simon J; Cairney, Scott A; Lewis, Penelope A

    2016-05-01

    Extracting regularities from a sequence of events is essential for understanding our environment. However, there is no consensus regarding the extent to which such regularities can be generalised beyond the modality of learning. One reason for this could be the variation in consolidation intervals used in different paradigms, also including an opportunity to sleep. Using a novel statistical learning paradigm in which structured information is acquired in the auditory domain and tested in the visual domain over either 30 min or 24 h consolidation intervals, we show that cross-modal transfer can occur, but this transfer is only seen in the 24 h group. Importantly, the extent of cross-modal transfer is predicted by the amount of slow wave sleep (SWS) obtained. Additionally, cross-modal transfer is associated with the same pattern of decreasing medial temporal lobe and increasing striatal involvement which has previously been observed to occur across 24 h in unimodal statistical learning. We also observed enhanced functional connectivity after 24 h in a network of areas which have been implicated in cross-modal integration including the precuneus and the middle occipital gyrus. Finally, functional connectivity between the striatum and the precuneus was also enhanced, and this strengthening was predicted by SWS. These results demonstrate that statistical learning can generalise to some extent beyond the modality of acquisition, and together with our previously published unimodal results, support the notion that statistical learning is both domain-general and domain-specific. PMID:27017231

  17. Complex Dynamics in Information Sharing Networks

    NASA Astrophysics Data System (ADS)

    Cronin, Bruce

    This study examines the roll-out of an electronic knowledge base in a medium-sized professional services firm over a six year period. The efficiency of such implementation is a key business problem in IT systems of this type. Data from usage logs provides the basis for analysis of the dynamic evolution of social networks around the depository during this time. The adoption pattern follows an "s-curve" and usage exhibits something of a power law distribution, both attributable to network effects, and network position is associated with organisational performance on a number of indicators. But periodicity in usage is evident and the usage distribution displays an exponential cut-off. Further analysis provides some evidence of mathematical complexity in the periodicity. Some implications of complex patterns in social network data for research and management are discussed. The study provides a case study demonstrating the utility of the broad methodological approach.

  18. Evaporative Mass Transfer Behavior of a Complex Immiscible Liquid

    PubMed Central

    McColl, Colleen M.; Johnson, Gwynn R.; Brusseau, Mark L.

    2010-01-01

    A series of laboratory experiments was conducted with a multiple-component immiscible liquid, collected from the Picillo Farm Superfund Site in Rhode Island, to examine liquid-vapor mass-transfer behavior. The immiscible liquid, which comprises solvents, oils, pesticides, PCBs, paint sludges, explosives, and other compounds, was characterized using gas chromatography and gas chromatography/mass spectrometry to determine mole fractions of selected constituents. Batch experiments were conducted to evaluate equilibrium phase-partitioning behavior. Two sets of air-stripping column studies were conducted to examine the mass-transfer dynamics of five selected target compounds present in the immiscible-liquid mixture. One set of column experiments was designed to represent a system with free-phase immiscible liquid present; the other was designed to represent a system with a residual phase of immiscible liquid. Initial elution behavior of all target components generally appeared to be ideal for both systems, as the initial vapor-phase concentrations were similar to vapor-phase concentrations measured for the batch experiment and those estimated using Raoult’s law (incorporating the immiscible-liquid composition data). Later-stage removal of 1,2-dichlorobenzene appeared to be rate limited for the columns containing free-phase immiscible liquid and no porous medium. Conversely, evaporative mass transfer appeared to be ideal throughout the experiment conducted with immiscible liquid distributed relatively uniformly as a residual phase within a sandy porous medium. PMID:18614196

  19. Structural Allostery and Binding of the Transferring Receptor Complex

    SciTech Connect

    Xu,G.; Liu, R.; Zak, O.; Aisen, P.; Chance, M.

    2005-01-01

    The structural allostery and binding interface for the human serum transferrin (Tf){center_dot}transferrin receptor (TfR) complex were identified using radiolytic footprinting and mass spectrometry. We have determined previously that the transferrin C-lobe binds to the receptor helical domain. In this study we examined the binding interactions of full-length transferrin with receptor and compared these data with a model of the complex derived from cryoelectron microscopy (cryo-EM) reconstructions. The footprinting results provide the following novel conclusions. First, we report characteristic oxidations of acidic residues in the C-lobe of native Tf and basic residues in the helical domain of TfR that were suppressed as a function of complex formation; this confirms ionic interactions between these protein segments as predicted by cryo-EM data and demonstrates a novel method for detecting ion pair interactions in the formation of macromolecular complexes. Second, the specific side-chain interactions between the C-lobe and N-lobe of transferrin and the corresponding interactions sites on the transferrin receptor predicted from cryo-EM were confirmed in solution. Last, the footprinting data revealed allosteric movements of the iron binding C- and N-lobes of Tf that sequester iron as a function of complex formation; these structural changes promote tighter binding of the metal ion and facilitate efficient ion transport during endocytosis.

  20. MA-9 ASTRONAUT L. GORDON COOPER LEAVES TRANSFER VAN AT LAUNCH COMPLEX 14

    NASA Technical Reports Server (NTRS)

    1963-01-01

    MA-9 ASTRONAUT L. GORDON COOPER LEAVES TRANSFER VAN AT LAUNCH COMPLEX 14 S-63-6247 P-07136, ARCHIVE-03808 Astronaut L. Gordon Cooper, Jr., leaves the transfer van at Pad #14 for his ride up the gantry elevator to the 11th deck where he will be inserted into the spacecraft for his 22-orbit mission.

  1. Electrical conduction in organic charge transfer complexes under pressure: A theoretical view

    NASA Astrophysics Data System (ADS)

    Singh, Yadunath

    2016-05-01

    We propose a theoretical view of temperature dependent electrical conductivity in organic charge transfer complexes and radical ion salts. Understanding of the basic conduction mechanism under high pressure in these systems is our aim. The mechanism is discussed mainly on the basis of molecular orbital overlap theory, role of charge transfer forces and charge density waves etc.

  2. Picosecond spectroscopy of charge-transfer processes. Photochemistry of anthracene-tetranitromethane EDA complexes

    NASA Astrophysics Data System (ADS)

    Masnovi, J. M.; Huffman, J. C.; Kochi, J. K.; Hilinski, E. F.; Rentzepis, P. M.

    1984-04-01

    The temporal sequence of events that follow 532 nm excitation of electron donor-acceptor, EDA, complexes of several substituted anthracenes with tetranitromethane is monitored by means of picosecond spectroscopy. Excitation of the charge-transfer band of these EDA complexes produces high yields of 1 : 1 adducts. Absorption spectra and kinetics of the transient species involved in these photochemical reactions provide the basis for elucidation of the reaction mechanism following charge-transfer excitation to the ion pairs.

  3. Fluorescence energy transfer in quantum dot/azo dye complexes in polymer track membranes

    NASA Astrophysics Data System (ADS)

    Gromova, Yulia A.; Orlova, Anna O.; Maslov, Vladimir G.; Fedorov, Anatoly V.; Baranov, Alexander V.

    2013-10-01

    Fluorescence resonance energy transfer in complexes of semiconductor CdSe/ZnS quantum dots with molecules of heterocyclic azo dyes, 1-(2-pyridylazo)-2-naphthol and 4-(2-pyridylazo) resorcinol, formed at high quantum dot concentration in the polymer pore track membranes were studied by steady-state and transient PL spectroscopy. The effect of interaction between the complexes and free quantum dots on the efficiency of the fluorescence energy transfer and quantum dot luminescence quenching was found and discussed.

  4. Technology, Information and Organization; Information Transfer in Industrial R and D.

    ERIC Educational Resources Information Center

    Rosenbloom, Richard S.; Wolek, Francis W.

    This is a study of information transfer in the R and D operations of large industrial corporations. Its basis is a body of survey data collected from 2000 engineers and scientists in 13 establishments of four corporations and from 1200 members of the Institute of Electrical and Electronics Engineers. The data describe instances in which…

  5. Information transfer across the scales of climate data variability

    NASA Astrophysics Data System (ADS)

    Palus, Milan; Jajcay, Nikola; Hartman, David; Hlinka, Jaroslav

    2015-04-01

    Multitude of scales characteristic of the climate system variability requires innovative approaches in analysis of instrumental time series. We present a methodology which starts with a wavelet decomposition of a multi-scale signal into quasi-oscillatory modes of a limited band-with, described using their instantaneous phases and amplitudes. Then their statistical associations are tested in order to search for interactions across time scales. In particular, an information-theoretic formulation of the generalized, nonlinear Granger causality is applied together with surrogate data testing methods [1]. The method [2] uncovers causal influence (in the Granger sense) and information transfer from large-scale modes of climate variability with characteristic time scales from years to almost a decade to regional temperature variability on short time scales. In analyses of daily mean surface air temperature from various European locations an information transfer from larger to smaller scales has been observed as the influence of the phase of slow oscillatory phenomena with periods around 7-8 years on amplitudes of the variability characterized by smaller temporal scales from a few months to annual and quasi-biennial scales [3]. In sea surface temperature data from the tropical Pacific area an influence of quasi-oscillatory phenomena with periods around 4-6 years on the variability on and near the annual scale has been observed. This study is supported by the Ministry of Education, Youth and Sports of the Czech Republic within the Program KONTAKT II, Project No. LH14001. [1] M. Palus, M. Vejmelka, Phys. Rev. E 75, 056211 (2007) [2] M. Palus, Entropy 16(10), 5263-5289 (2014) [3] M. Palus, Phys. Rev. Lett. 112, 078702 (2014)

  6. New scaling relation for information transfer in biological networks.

    PubMed

    Kim, Hyunju; Davies, Paul; Walker, Sara Imari

    2015-12-01

    We quantify characteristics of the informational architecture of two representative biological networks: the Boolean network model for the cell-cycle regulatory network of the fission yeast Schizosaccharomyces pombe (Davidich et al. 2008 PLoS ONE 3, e1672 (doi:10.1371/journal.pone.0001672)) and that of the budding yeast Saccharomyces cerevisiae (Li et al. 2004 Proc. Natl Acad. Sci. USA 101, 4781-4786 (doi:10.1073/pnas.0305937101)). We compare our results for these biological networks with the same analysis performed on ensembles of two different types of random networks: Erdös-Rényi and scale-free. We show that both biological networks share features in common that are not shared by either random network ensemble. In particular, the biological networks in our study process more information than the random networks on average. Both biological networks also exhibit a scaling relation in information transferred between nodes that distinguishes them from random, where the biological networks stand out as distinct even when compared with random networks that share important topological properties, such as degree distribution, with the biological network. We show that the most biologically distinct regime of this scaling relation is associated with a subset of control nodes that regulate the dynamics and function of each respective biological network. Information processing in biological networks is therefore interpreted as an emergent property of topology (causal structure) and dynamics (function). Our results demonstrate quantitatively how the informational architecture of biologically evolved networks can distinguish them from other classes of network architecture that do not share the same informational properties. PMID:26701883

  7. Dynamical Theory of Charge Transfer Between Complex Atoms and Surfaces

    NASA Astrophysics Data System (ADS)

    Chaudhuri, Basudev; Marston, Brad

    2000-03-01

    An existing dynamical quantum many-body theory of charge transfer(A. V. Onufriev and J. B. Marston, Phys. Rev. B 53), 13340 (1996); J. Merino and J. B. Marston, Phys. Rev. B 58, 6982 (1998). describes atoms with simple s-orbitals, such as alkalis and alkaline-earths, interacting with metal surfaces. The many-body equations of motion (EOM) are developed systematically as an expansion in the number of surface particle-hole excitations. Here we generalize this theory to describe atoms with richer orbital structures, such as atomic oxygen. In the simplest version of the model, only the single-particle p_z-orbitals of the atom, the ones oriented perpendicular to the surface, participate directly in resonant charge transfer as they have the largest overlap with the metallic wavefunctions. However, as the several-electron Russell-Saunders eigenstates, labeled by total angular momenta quantum numbers J, L, and S, are built out of products of single-particle orbitals, non-trivial matrix elements must be incorporated into the many-body EOM's. Comparison to recent experimental results(A. C. Lavery, C. E. Sosolik, and B. H. Cooper, Nucl. Instrum. Meth. B 157), 42 (1999); A. C. Lavery et al. to appear in Phys. Rev. B. on the scattering of low-energy oxygen ions off Cu(001) surfaces is made.

  8. Electrostatic effects on electron-transfer kinetics in the cytochrome f-plastocyanin complex.

    PubMed Central

    Soriano, G M; Cramer, W A; Krishtalik, L I

    1997-01-01

    In a complex of two electron-transfer proteins, their redox potentials can be shifted due to changes in the dielectric surroundings and the electrostatic potentials at each center caused by the charged residues of the partner. These effects are dependent on the geometry of the complex. Three different docking configurations (DCs) for intracomplex electron transfer between cytochrome f and plastocyanin were studied, defined by 1) close contact of the positively charged region of cytochrome f and the negatively charged regions of plastocyanin (DC1) and by (2, 3) close contact of the surface regions adjacent to the Fe and Cu redox centers (DC2 and DC3). The equilibrium energetics for electron transfer in DC1-DC3 are the same within approximately +/-0.1 kT. The lower reorganization energy for DC2 results in a slightly lower activation energy for this complex compared with DC1 and DC3. The long heme-copper distance (approximately 24 A) in the DC1 complex drastically decreases electronic coupling and makes this complex much less favorable for electron transfer than DC2 or DC3. DC1-like complexes can only serve as docking intermediates in the pathway toward formation of an electron-transfer-competent complex. Elimination of the four positive charges arising from the lysine residues in the positive patch of cytochrome f, as accomplished by mutagenesis, exerts a negligible effect (approximately 3 mV) on the redox potential difference between cyt f and PC. PMID:9414237

  9. Suppression of electron transfer to dioxygen by charge transfer and electron transfer complexes in the FAD-dependent reductase component of toluene dioxygenase.

    PubMed

    Lin, Tzong-Yuan; Werther, Tobias; Jeoung, Jae-Hun; Dobbek, Holger

    2012-11-01

    The three-component toluene dioxygenase system consists of an FAD-containing reductase, a Rieske-type [2Fe-2S] ferredoxin, and a Rieske-type dioxygenase. The task of the FAD-containing reductase is to shuttle electrons from NADH to the ferredoxin, a reaction the enzyme has to catalyze in the presence of dioxygen. We investigated the kinetics of the reductase in the reductive and oxidative half-reaction and detected a stable charge transfer complex between the reduced reductase and NAD(+) at the end of the reductive half-reaction, which is substantially less reactive toward dioxygen than the reduced reductase in the absence of NAD(+). A plausible reason for the low reactivity toward dioxygen is revealed by the crystal structure of the complex between NAD(+) and reduced reductase, which shows that the nicotinamide ring and the protein matrix shield the reactive C4a position of the isoalloxazine ring and force the tricycle into an atypical planar conformation, both factors disfavoring the reaction of the reduced flavin with dioxygen. A rapid electron transfer from the charge transfer complex to electron acceptors further reduces the risk of unwanted side reactions, and the crystal structure of a complex between the reductase and its cognate ferredoxin shows a short distance between the electron-donating and -accepting cofactors. Attraction between the two proteins is likely mediated by opposite charges at one large patch of the complex interface. The stability, specificity, and reactivity of the observed charge transfer and electron transfer complexes are thought to prevent the reaction of reductase(TOL) with dioxygen and thus present a solution toward conflicting requirements. PMID:22992736

  10. Path induced coherent energy transfer in light-harvesting complexes in purple bacteria

    NASA Astrophysics Data System (ADS)

    Sun, Kewei; Ye, Jun; Zhao, Yang

    2014-09-01

    Features of path dependent energy transfer in a dual-ring light-harvesting (LH2) complexes (B850) system have been examined in detail systematically. The Frenkel-Dirac time dependent variational method with the Davydov D1 Ansatz is employed with detailed evolution of polaron dynamics in real space readily obtained. It is found that the phase of the transmission amplitude through the LH2 complexes plays an important role in constructing the coherent excitonic energy transfer. It is also found that the symmetry breaking caused by the dimerization of bacteriochlorophylls and coherence or correlation between two rings will be conducive in enhancing the exciton transfer efficiency.

  11. Path induced coherent energy transfer in light-harvesting complexes in purple bacteria.

    PubMed

    Sun, Kewei; Ye, Jun; Zhao, Yang

    2014-09-28

    Features of path dependent energy transfer in a dual-ring light-harvesting (LH2) complexes (B850) system have been examined in detail systematically. The Frenkel-Dirac time dependent variational method with the Davydov D1 Ansatz is employed with detailed evolution of polaron dynamics in real space readily obtained. It is found that the phase of the transmission amplitude through the LH2 complexes plays an important role in constructing the coherent excitonic energy transfer. It is also found that the symmetry breaking caused by the dimerization of bacteriochlorophylls and coherence or correlation between two rings will be conducive in enhancing the exciton transfer efficiency. PMID:25273408

  12. Transfer of Declarative Knowledge in Complex Information-Processing Domains.

    ERIC Educational Resources Information Center

    Harvey, Leon; Anderson, John

    1996-01-01

    Two experiments tested the hypothesis that subjects introduced to a first programming language develop a representation of basic programming concepts that help them integrate new declarative knowledge from a second programming language. The effect on reading was greater for pages that were conceptually close across texts and for subjects who had…

  13. Excitation energy transfer in photosynthetic protein-pigment complexes

    NASA Astrophysics Data System (ADS)

    Yeh, Shu-Hao

    Quantum biology is a relatively new research area which investigates the rules that quantum mechanics plays in biology. One of the most intriguing systems in this field is the coherent excitation energy transport (EET) in photosynthesis. In this document I will discuss the theories that are suitable for describing the photosynthetic EET process and the corresponding numerical results on several photosynthetic protein-pigment complexes (PPCs). In some photosynthetic EET processes, because of the electronic coupling between the chromophores within the system is about the same order of magnitude as system-bath coupling (electron-phonon coupling), a non-perturbative method called hierarchy equation of motion (HEOM) is applied to study the EET dynamics. The first part of this thesis includes brief introduction and derivation to the HEOM approach. The second part of this thesis the HEOM method will be applied to investigate the EET process within the B850 ring of the light harvesting complex 2 (LH2) from purple bacteria, Rhodopseudomonas acidophila. The dynamics of the exciton population and coherence will be analyzed under different initial excitation configurations and temperatures. Finally, how HEOM can be implemented to simulate the two-dimensional electronic spectra of photosynthetic PPCs will be discussed. Two-dimensional electronic spectroscopy is a crucial experimental technique to probe EET dynamics in multi-chromophoric systems. The system we are interested in is the 7-chromophore Fenna-Matthews-Olson (FMO) complex from green sulfur bacteria, Prosthecochloris aestuarii. Recent crystallographic studies report the existence of an additional (eighth) chromophore in some of the FMO monomers. By applying HEOM we are able to calculate the two-dimensional electronic spectra of the 7-site and 8-site FMO complexes and investigate the functionality of the eighth chromophore.

  14. Conditions for Lorentz-invariant superluminal information transfer without signaling

    NASA Astrophysics Data System (ADS)

    Grössing, G.; Fussy, S.; Mesa Pascasio, J.; Schwabl, H.

    2016-03-01

    We understand emergent quantum mechanics in the sense that quantum mechanics describes processes of physical emergence relating an assumed sub-quantum physics to macroscopic boundary conditions. The latter can be shown to entail top-down causation, in addition to usual bottom-up scenarios. With this example it is demonstrated that definitions of “realism” in the literature are simply too restrictive. A prevailing manner to define realism in quantum mechanics is in terms of pre-determination independent of the measurement. With our counter-example, which actually is ubiquitous in emergent, or self-organizing, systems, we argue for realism without pre-determination. We refer to earlier results of our group showing how the guiding equation of the de Broglie-Bohm interpretation can be derived from a theory with classical ingredients only. Essentially, this corresponds to a “quantum mechanics without wave functions” in ordinary 3-space, albeit with nonlocal correlations. This, then, leads to the central question of how to deal with the nonlocality problem in a relativistic setting. We here show that a basic argument discussing the allegedly paradox time ordering of events in EPR-type two-particle experiments falls short of taking into account the contextuality of the experimental setup. Consequently, we then discuss under which circumstances (i.e. physical premises) superluminal information transfer (but not signaling) may be compatible with a Lorentz-invariant theory. Finally, we argue that the impossibility of superluminal signaling - despite the presence of superluminal information transfer - is not the result of some sort of conspiracy (á la “Nature likes to hide”), but the consequence of the impossibility to exactly reproduce in repeated experimental runs a state's preparation, or of the no-cloning theorem, respectively.

  15. Intermolecular hydrogen bond complexes by in situ charge transfer complexation of o-tolidine with picric and chloranilic acids

    NASA Astrophysics Data System (ADS)

    Refat, Moamen S.; Saad, Hosam A.; Adam, Abdel Majid A.

    2011-08-01

    A two new charge transfer complexes formed from the interactions between o-tolidine (o-TOL) and picric (PA) or chloranilic (CA) acids, with the compositions, [(o-TOL)(PA) 2] and [(o-TOL)(CA) 2] have been prepared. The 13C NMR, 1H NMR, 1H-Cosy, and IR show that the charge-transfer chelation occurs via the formation of chain structures O-H⋯N intermolecular hydrogen bond between 2NH 2 groups of o-TOL molecule and OH group in each PA or CA units. Photometric titration measurements concerning the two reactions in methanol were performed and the measurements show that the donor-acceptor molar ratio was found to be 1:2 using the modified Benesi-Hildebrand equation. The spectroscopic data were discussed in terms of formation constant, molar extinction coefficient, oscillator strength, dipole moment, standard free energy, and ionization potential. Thermal behavior of both charge transfer complexes showed that the complexes were more stable than their parents. The thermodynamic parameters were estimated from the differential thermogravimetric curves. The results indicated that the formation of molecular charge transfer complexes is spontaneous and endothermic.

  16. Using metal complex-labeled peptides for charge transfer-based biosensing with semiconductor quantum dots

    NASA Astrophysics Data System (ADS)

    Medintz, Igor L.; Pons, Thomas; Trammell, Scott A.; Blanco-Canosa, Juan B.; Dawson, Philip E.; Mattoussi, Hedi

    2009-02-01

    Luminescent colloidal semiconductor quantum dots (QDs) have unique optical and photonic properties and are highly sensitive to charge transfer in their surrounding environment. In this study we used synthetic peptides as physical bridges between CdSe-ZnS core-shell QDs and some of the most common redox-active metal complexes to understand the charge transfer interactions between the metal complexes and QDs. We found that QD emission underwent quenching that was highly dependent on the choice of metal complex used. We also found that quenching traces the valence or number of metal complexes brought into close proximity of the nanocrystal surface. Monitoring of the QD absorption bleaching in the presence of the metal complex provided insight into the charge transfer mechanism. The data suggest that two distinct charge transfer mechanisms can take place. One directly to the QD core states for neutral capping ligands and a second to surface states for negatively charged capping ligands. A basic understanding of the proximity driven charge-transfer and quenching interactions allowed us to construct proteolytic enzyme sensing assemblies with the QD-peptide-metal complex conjugates.

  17. Charge-transfer complexes of pyrimidine Schiff bases with aromatic nitro compounds

    NASA Astrophysics Data System (ADS)

    Issa, Yousry M.; El Ansary, A. L.; Sherif, O. E.; Hassib, H. B.

    2011-08-01

    Charge-transfer (CT) complexes of pyrimidine Schiff bases, derived from condensation of 2-aminopyrimidine and substituted benzaldehydes, with some aromatic polynitro compounds were prepared and investigated using IR, UV, visible and 1H NMR spectroscopy. For all solid complexes, the main interaction between the donor and acceptor molecules takes place through the π-π* interaction. Strong and some weak acidic acceptors, in addition interact through proton transfer from the acceptor molecule to the basic centre of the electron donor. Also, an n-π* transition was detected in some complexes.

  18. Charge-transfer complexes of pyrimidine Schiff bases with aromatic nitro compounds.

    PubMed

    Issa, Yousry M; el-Ansary, A L; Sherif, O E; Hassib, H B

    2011-08-01

    Charge-transfer (CT) complexes of pyrimidine Schiff bases, derived from condensation of 2-aminopyrimidine and substituted benzaldehydes, with some aromatic polynitro compounds were prepared and investigated using IR, UV, visible and (1)H NMR spectroscopy. For all solid complexes, the main interaction between the donor and acceptor molecules takes place through the π-π* interaction. Strong and some weak acidic acceptors, in addition interact through proton transfer from the acceptor molecule to the basic centre of the electron donor. Also, an n-π* transition was detected in some complexes. PMID:21531169

  19. Beyond Course-to-Course: New Information On Program Transfer. The Advisor

    ERIC Educational Resources Information Center

    British Columbia Council on Admissions and Transfer, 2003

    2003-01-01

    "The Advisor" provides important information or "system alerts," in user-friendly format and language, on issues and changes affecting admissions and transfer. This document outlines where in the BC Transfer Guide to locate information on transferring between specific programs at different institutions. Please note this document was published…

  20. 77 FR 12840 - Federal Supply Service; Information Collection; Standard Form (SF) 123, Transfer Order-Surplus...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-03-02

    ... ADMINISTRATION Federal Supply Service; Information Collection; Standard Form (SF) 123, Transfer Order-Surplus... regarding Standard Form (SF) 123, transfer order-surplus personal property and continuation sheet. Public... Information Collection 3090- 0014, Standard Form (SF) 123, Transfer Order--Surplus Personal Property...

  1. Quantum coherent energy transfer over varying pathways in single light-harvesting complexes.

    PubMed

    Hildner, Richard; Brinks, Daan; Nieder, Jana B; Cogdell, Richard J; van Hulst, Niek F

    2013-06-21

    The initial steps of photosynthesis comprise the absorption of sunlight by pigment-protein antenna complexes followed by rapid and highly efficient funneling of excitation energy to a reaction center. In these transport processes, signatures of unexpectedly long-lived coherences have emerged in two-dimensional ensemble spectra of various light-harvesting complexes. Here, we demonstrate ultrafast quantum coherent energy transfer within individual antenna complexes of a purple bacterium under physiological conditions. We find that quantum coherences between electronically coupled energy eigenstates persist at least 400 femtoseconds and that distinct energy-transfer pathways that change with time can be identified in each complex. Our data suggest that long-lived quantum coherence renders energy transfer in photosynthetic systems robust in the presence of disorder, which is a prerequisite for efficient light harvesting. PMID:23788794

  2. Metal complex-based electron-transfer mediators in dye-sensitized solar cells

    DOEpatents

    Elliott, C. Michael; Sapp, Shawn A.; Bignozzi, Carlo Alberto; Contado, Cristiano; Caramori, Stefano

    2006-03-28

    This present invention provides a metal-ligand complex and methods for using and preparing the same. In particular, the metal-ligand complex of the present invention is of the formula: L.sub.a-M-X.sub.b where L, M, X, a, and b are those define herein. The metal-ligand complexes of the present invention are useful in a variety of applications including as electron-transfer mediators in dye-sensitized solar cells and related photoelectrochromic devices.

  3. Structure and staging in polyacetylene charge-transfer complexes

    NASA Astrophysics Data System (ADS)

    Murthy, N. S.; Shacklette, L. W.; Baughman, R. H.

    1989-10-01

    A structure is proposed for a stage-2 complex of polyacetylene which contains potassium as the dopant ion. This structure utilizes as a basic motif an alkali-metal column surrounded by four polyacetylene chains; this motif is also found in the tetragonal phase that appears at higher dopant concentrations. In the new structure, each polyacetylene is adjacent to one alkali-metal column, so the phase contains four polymer chains per alkali-metal column as compared with two chains per column for the tetragonal phase. X-ray diffraction and electrochemical data show that a mixture of undoped and doped phases are present at low dopant concentrations. In light of these results, general aspects of staging in n-doped and p-doped polyacetylene are discussed.

  4. The directional flow of visual information transfer between pedestrians

    PubMed Central

    Gallup, Andrew C.; Chong, Andrew; Couzin, Iain D.

    2012-01-01

    Close behavioural coupling of visual orientation may provide a range of adaptive benefits to social species. In order to investigate the natural properties of gaze-following between pedestrians, we displayed an attractive stimulus in a frequently trafficked corridor within which a hidden camera was placed to detect directed gaze from passers-by. The presence of visual cues towards the stimulus by nearby pedestrians increased the probability of passers-by looking as well. In contrast to cueing paradigms used for laboratory research, however, we found that individuals were more responsive to changes in the visual orientation of those walking in the same direction in front of them (i.e. viewing head direction from behind). In fact, visual attention towards the stimulus diminished when oncoming pedestrians had previously looked. Information was therefore transferred more effectively behind, rather than in front of, gaze cues. Further analyses show that neither crowding nor group interactions were driving these effects, suggesting that, within natural settings gaze-following is strongly mediated by social interaction and facilitates acquisition of environmentally relevant information. PMID:22456331

  5. The origin and dynamic evolution of chemical information transfer

    PubMed Central

    Steiger, Sandra; Schmitt, Thomas; Schaefer, H. Martin

    2011-01-01

    Although chemical communication is the most widespread form of communication, its evolution and diversity are not well understood. By integrating studies of a wide range of terrestrial plants and animals, we show that many chemicals are emitted, which can unintentionally provide information (cues) and, therefore, act as direct precursors for the evolution of intentional communication (signals). Depending on the content, design and the original function of the cue, there are predictable ways that selection can enhance the communicative function of chemicals. We review recent progress on how efficacy-based selection by receivers leads to distinct evolutionary trajectories of chemical communication. Because the original function of a cue may channel but also constrain the evolution of functional communication, we show that a broad perspective on multiple selective pressures acting upon chemicals provides important insights into the origin and dynamic evolution of chemical information transfer. Finally, we argue that integrating chemical ecology into communication theory may significantly enhance our understanding of the evolution, the design and the content of signals in general. PMID:21177681

  6. Why are the Interaction Energies of Charge-Transfer Complexes Challenging for DFT?

    PubMed

    Steinmann, Stephan N; Piemontesi, Cyril; Delachat, Aurore; Corminboeuf, Clemence

    2012-05-01

    The description of ground state charge-transfer complexes is highly challenging. Illustrative examples include large overestimations of charge-transfer by local and semilocal density functional approximations as well as inaccurate binding energies. It is demonstrated here that standard density functionals fail to accurately describe interaction energies of charge-transfer complexes not only because of the missing long-range exchange as generally assumed but also as a result of the neglect of weak interactions. Thus, accounting for the missing van der Waals interactions is of key importance. These assertions, based on the evaluation of the extent of stabilization due to dispersion using both DFT coupled with our recent density-dependent dispersion correction (dDsC) and high-level ab initio computations, reflect the imperfect error-cancellation between the overestimation of charge-transfer and the missing long-range interactions. An in-depth energy decomposition analysis of an illustrative series of four small ambidentate molecules (HCN, HNC, HF, and ClF) bound together with NF3 provides the main conclusions, which are validated on a prototypical organic charge-transfer complex (i.e., tetrathiafulvalene-tetracyanoquinodimethane, TTF-TCNQ). We establish that the interaction energies for charge-transfer complexes can only be properly described when using well-balanced functionals such as PBE0-dDsC, M06-2X, and LC-BOP-LRD. PMID:26593656

  7. Cholesteryl ester transfer between lipoproteins does not require a ternary tunnel complex with CETP.

    PubMed

    Lauer, Matthias E; Graff-Meyer, Alexandra; Rufer, Arne C; Maugeais, Cyrille; von der Mark, Elisabeth; Matile, Hugues; D'Arcy, Brigitte; Magg, Christine; Ringler, Philippe; Müller, Shirley A; Scherer, Sebastian; Dernick, Gregor; Thoma, Ralf; Hennig, Michael; Niesor, Eric J; Stahlberg, Henning

    2016-05-01

    The cholesteryl ester transfer protein (CETP) enables the transfer of cholesteryl ester (CE) from high-density lipoproteins (HDL) to low-density lipoproteins (LDL) in the plasma compartment. CETP inhibition raises plasma levels of HDL cholesterol; a ternary tunnel complex with CETP bridging HDL and LDL was suggested as a mechanism. Here, we test whether the inhibition of CETP tunnel complex formation is a promising approach to suppress CE transfer from HDL to LDL, for potential treatment of cardio-vascular disease (CVD). Three monoclonal antibodies against different epitopes of CETP are assayed for their potential to interfere with CE transfer between HDL and/or LDL. Surprisingly, antibodies that target the tips of the elongated CETP molecule, interaction sites sterically required to form the suggested transfer complexes, do not interfere with CETP activity, but an antibody binding to the central region does. We show that CETP interacts with HDL, but not with LDL. Our findings demonstrate that a ternary tunnel complex is not the mechanistic prerequisite to transfer CE among lipoproteins. PMID:26876146

  8. (Comparison of group transfer, inner shere and outer sphere electron transfer mechanisms for organometallic complexes)

    SciTech Connect

    Not Available

    1991-01-01

    Our studies of reactions of metal carbonyl cations and anions have shown that metal carbonyl cations can catalyze CO exchange reactions on metal carbonyl anions. This result provides further evidence for a mechanism involving attack of the metal carbonyl anion on a carbon of the metal carbonyl cation in CO{sup 2+} transfer reactions. Reaction of metal carbonyl anions with metal carbonyl halides is a common approach to formation of metal-metal bonds. We have begun to use kinetic data and product analysis to understand the formation of homobimetallic versus heterobimetallic products in such reactions. Initial data indicate a nucleophilic attack, possibly through a ring-slippage mechanism.

  9. [Comparison of group transfer, inner shere and outer sphere electron transfer mechanisms for organometallic complexes]. Summary

    SciTech Connect

    Not Available

    1991-12-31

    Our studies of reactions of metal carbonyl cations and anions have shown that metal carbonyl cations can catalyze CO exchange reactions on metal carbonyl anions. This result provides further evidence for a mechanism involving attack of the metal carbonyl anion on a carbon of the metal carbonyl cation in CO{sup 2+} transfer reactions. Reaction of metal carbonyl anions with metal carbonyl halides is a common approach to formation of metal-metal bonds. We have begun to use kinetic data and product analysis to understand the formation of homobimetallic versus heterobimetallic products in such reactions. Initial data indicate a nucleophilic attack, possibly through a ring-slippage mechanism.

  10. Complex Geometry Creation and Turbulent Conjugate Heat Transfer Modeling

    SciTech Connect

    Bodey, Isaac T; Arimilli, Rao V; Freels, James D

    2011-01-01

    The multiphysics capabilities of COMSOL provide the necessary tools to simulate the turbulent thermal-fluid aspects of the High Flux Isotope Reactor (HFIR). Version 4.1, and later, of COMSOL provides three different turbulence models: the standard k-{var_epsilon} closure model, the low Reynolds number (LRN) k-{var_epsilon} model, and the Spalart-Allmaras model. The LRN meets the needs of the nominal HFIR thermal-hydraulic requirements for 2D and 3D simulations. COMSOL also has the capability to create complex geometries. The circular involute fuel plates used in the HFIR require the use of algebraic equations to generate an accurate geometrical representation in the simulation environment. The best-estimate simulation results show that the maximum fuel plate clad surface temperatures are lower than those predicted by the legacy thermal safety code used at HFIR by approximately 17 K. The best-estimate temperature distribution determined by COMSOL was then used to determine the necessary increase in the magnitude of the power density profile (PDP) to produce a similar clad surface temperature as compared to the legacy thermal safety code. It was determined and verified that a 19% power increase was sufficient to bring the two temperature profiles to relatively good agreement.

  11. Carotenoid charge transfer states and their role in energy transfer processes in LH1-RC complexes from aerobic anoxygenic phototrophs.

    PubMed

    Šlouf, Václav; Fuciman, Marcel; Dulebo, Alexander; Kaftan, David; Koblížek, Michal; Frank, Harry A; Polívka, Tomáš

    2013-09-26

    Light-harvesting complexes ensure necessary flow of excitation energy into photosynthetic reaction centers. In the present work, transient absorption measurements were performed on LH1-RC complexes isolated from two aerobic anoxygenic phototrophs (AAPs), Roseobacter sp. COL2P containing the carotenoid spheroidenone, and Erythrobacter sp. NAP1 which contains the carotenoids zeaxanthin and bacteriorubixanthinal. We show that the spectroscopic data from the LH1-RC complex of Roseobacter sp. COL2P are very similar to those previously reported for Rhodobacter sphaeroides, including the transient absorption spectrum originating from the intramolecular charge-transfer (ICT) state of spheroidenone. Although the ICT state is also populated in LH1-RC complexes of Erythrobacter sp. NAP1, its appearance is probably related to the polarity of the bacteriorubixanthinal environment rather than to the specific configuration of the carotenoid, which we hypothesize is responsible for populating the ICT state of spheroidenone in LH1-RC of Roseobacter sp. COL2P. The population of the ICT state enables efficient S1/ICT-to-bacteriochlorophyll (BChl) energy transfer which would otherwise be largely inhibited for spheroidenone and bacteriorubixanthinal due to their low energy S1 states. In addition, the triplet states of these carotenoids appear well-tuned for efficient quenching of singlet oxygen or BChl-a triplets, which is of vital importance for oxygen-dependent organisms such as AAPs. PMID:23130956

  12. Measurement of Information-Based Complexity in Listening.

    ERIC Educational Resources Information Center

    Bishop, Walton B.

    When people say that what they hear is "over their heads," they are describing a severe information-based complexity (I-BC) problem. They cannot understand what is said because some of the information needed is missing, contaminated, and/or costly to obtain. Students often face these I-BC problems, and teachers often exacerbate them. Yet listeners…

  13. Integrated information storage and transfer with a coherent magnetic device

    PubMed Central

    Jia, Ning; Banchi, Leonardo; Bayat, Abolfazl; Dong, Guangjiong; Bose, Sougato

    2015-01-01

    Quantum systems are inherently dissipation-less, making them excellent candidates even for classical information processing. We propose to use an array of large-spin quantum magnets for realizing a device which has two modes of operation: memory and data-bus. While the weakly interacting low-energy levels are used as memory to store classical information (bits), the high-energy levels strongly interact with neighboring magnets and mediate the spatial movement of information through quantum dynamics. Despite the fact that memory and data-bus require different features, which are usually prerogative of different physical systems – well isolation for the memory cells, and strong interactions for the transmission – our proposal avoids the notorious complexity of hybrid structures. The proposed mechanism can be realized with different setups. We specifically show that molecular magnets, as the most promising technology, can implement hundreds of operations within their coherence time, while adatoms on surfaces probed by a scanning tunneling microscope is a future possibility. PMID:26347152

  14. Integrated information storage and transfer with a coherent magnetic device.

    PubMed

    Jia, Ning; Banchi, Leonardo; Bayat, Abolfazl; Dong, Guangjiong; Bose, Sougato

    2015-01-01

    Quantum systems are inherently dissipation-less, making them excellent candidates even for classical information processing. We propose to use an array of large-spin quantum magnets for realizing a device which has two modes of operation: memory and data-bus. While the weakly interacting low-energy levels are used as memory to store classical information (bits), the high-energy levels strongly interact with neighboring magnets and mediate the spatial movement of information through quantum dynamics. Despite the fact that memory and data-bus require different features, which are usually prerogative of different physical systems--well isolation for the memory cells, and strong interactions for the transmission--our proposal avoids the notorious complexity of hybrid structures. The proposed mechanism can be realized with different setups. We specifically show that molecular magnets, as the most promising technology, can implement hundreds of operations within their coherence time, while adatoms on surfaces probed by a scanning tunneling microscope is a future possibility. PMID:26347152

  15. A novel approach to characterize information radiation in complex networks

    NASA Astrophysics Data System (ADS)

    Wang, Xiaoyang; Wang, Ying; Zhu, Lin; Li, Chao

    2016-06-01

    The traditional research of information dissemination is mostly based on the virus spreading model that the information is being spread by probability, which does not match very well to the reality, because the information that we receive is always more or less than what was sent. In order to quantitatively describe variations in the amount of information during the spreading process, this article proposes a safety information radiation model on the basis of communication theory, combining with relevant theories of complex networks. This model comprehensively considers the various influence factors when safety information radiates in the network, and introduces some concepts from the communication theory perspective, such as the radiation gain function, receiving gain function, information retaining capacity and information second reception capacity, to describe the safety information radiation process between nodes and dynamically investigate the states of network nodes. On a micro level, this article analyzes the influence of various initial conditions and parameters on safety information radiation through the new model simulation. The simulation reveals that this novel approach can reflect the variation of safety information quantity of each node in the complex network, and the scale-free network has better "radiation explosive power", while the small-world network has better "radiation staying power". The results also show that it is efficient to improve the overall performance of network security by selecting nodes with high degrees as the information source, refining and simplifying the information, increasing the information second reception capacity and decreasing the noises. In a word, this article lays the foundation for further research on the interactions of information and energy between internal components within complex systems.

  16. Perfect state transfers by selective quantum interferences within complex spin networks

    NASA Astrophysics Data System (ADS)

    Álvarez, Gonzalo A.; Mishkovsky, Mor; Danieli, Ernesto P.; Levstein, Patricia R.; Pastawski, Horacio M.; Frydman, Lucio

    2010-06-01

    We present a method that implements directional, perfect state transfers within a branched spin network by exploiting quantum interferences in the time domain. This method provides a tool for isolating subsystems from a large and complex one. Directionality is achieved by interrupting the spin-spin coupled evolution with periods of free Zeeman evolutions, whose timing is tuned to be commensurate with the relative phases accrued by specific spin pairs. This leads to a resonant transfer between the chosen qubits and to a detuning of all remaining pathways in the network, using only global manipulations. Since the transfer is perfect when the selected pathway is mediated by two or three spins, distant state transfers over complex networks can be achieved by successive recouplings among specific pairs or triads of spins. These effects are illustrated with a quantum simulator involving C13 NMR on leucine’s backbone; a six-spin network.

  17. Nonphotochemical Hole-Burning Studies of Energy Transfer Dynamics in Antenna Complexes of Photosynthetic Bacteria

    SciTech Connect

    Satoshi Matsuzaki

    2002-08-01

    This thesis contains the candidate's original work on excitonic structure and energy transfer dynamics of two bacterial antenna complexes as studied using spectral hole-burning spectroscopy. The general introduction is divided into two chapters (1 and 2). Chapter 1 provides background material on photosynthesis and bacterial antenna complexes with emphasis on the two bacterial antenna systems related to the thesis research. Chapter 2 reviews the underlying principles and mechanism of persistent nonphotochemical hole-burning (NPHB) spectroscopy. Relevant energy transfer theories are also discussed. Chapters 3 and 4 are papers by the candidate that have been published. Chapter 3 describes the application of NPHB spectroscopy to the Fenna-Matthews-Olson (FMO) complex from the green sulfur bacterium Prosthecochloris aestuarii; emphasis is on determination of the low energy vibrational structure that is important for understanding the energy transfer process associated within three lowest energy Qy-states of the complex. The results are compared with those obtained earlier on the FMO complex from Chlorobium tepidum. In Chapter 4, the energy transfer dynamics of the B800 molecules of intact LH2 and B800-deficient LH2 complexes of the purple bacterium Rhodopseudomonas acidophila are compared. New insights on the additional decay channel of the B800 ring of bacteriochlorophyll a (BChl a) molecules are provided. General conclusions are given in Chapter 5.

  18. Charge-Transfer Complex of p-Aminodiphenylamine with Maleic Anhydride: Spectroscopic, Electrochemical, and Physical Properties.

    PubMed

    Karaca, Erhan; Kaplan Can, Hatice; Bozkaya, Uğur; Özçiçek Pekmez, Nuran

    2016-07-01

    A new charge-transfer complex and the amide formed by the interaction between the electron donor of the p-aminodiphenylamine and the electron acceptor of maleic anhydride are investigated by spectroscopic methods. The amidation reaction is caused by proton and charge transfer between the maleic anhydride and p-aminodiphenylamine molecules. The Benesi-Hildebrand equation is used to determine the formation constant, the molar extinction coefficient and the standard Gibbs free energy of the complex by using UV/Vis spectroscopy. To reveal the electronic and spectroscopic properties of these molecules, theoretical computations are performed on the structures of maleic anhydride, p-aminodiphenylamine and the conformers of their charge-transfer complex. The charge-transfer complex and amidation reaction mechanism are also confirmed by IR and NMR spectroscopy and HRMS. The nature of the maleic anhydride-p-aminodiphenylamine complex is characterized by cyclic voltammetry, thermogravimetric analysis, XRD and SEM. Solid microribbons of this complex show higher thermal stability than p-aminodiphenylamine. PMID:26990700

  19. Information Center Complex publications and presentations, 1971-1980

    SciTech Connect

    Gill, A.B.; Hawthorne, S.W.

    1981-08-01

    This indexed bibliography lists publications and presentations of the Information Center Complex, Information Division, Oak Ridge National Laboratory, from 1971 through 1980. The 659 entries cover such topics as toxicology, air and water pollution, management and transportation of hazardous wastes, energy resources and conservation, and information science. Publications range in length from 1 page to 3502 pages and include topical reports, books, journal articles, fact sheets, and newsletters. Author, title, and group indexes are provided. Annual updates are planned.

  20. Photoelectric studies of the transmembrane charge transfer reactions in photosystem I pigment-protein complexes.

    PubMed

    Semenov, Alexey Yu; Mamedov, Mahir D; Chamorovsky, Sergey K

    2003-10-23

    The results of studies of charge transfer in cyanobacterial photosystem I (PS I) using the photoelectric method are reviewed. The electrogenicity in the PS I complex and its interaction with natural donors (plastocyanin, cytochrome c(6)), natural acceptors (ferredoxin, flavodoxin), or artificial acceptors and donors (methyl viologen and other redox dyes) were studied. The operating dielectric constant values in the vicinity of the charge transfer carriers in situ were calculated. The profile of distribution of the dielectric constant along the PS I pigment-protein complex (from plastocyanin or cytochrome c(6) through the chlorophyll dimer P700 to the acceptor complex) was estimated, and possible mechanisms of correlation between the local dielectric constant and electron transfer rate constant were discussed. PMID:14572628

  1. 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

  2. Quorum decision-making facilitates information transfer in fish shoals.

    PubMed

    Ward, Ashley J W; Sumpter, David J T; Couzin, Iain D; Hart, Paul J B; Krause, Jens

    2008-05-13

    Despite the growing interest in collective phenomena such as "swarm intelligence" and "wisdom of the crowds," little is known about the mechanisms underlying decision-making in vertebrate animal groups. How do animals use the behavior of others to make more accurate decisions, especially when it is not possible to identify which individuals possess pertinent information? One plausible answer is that individuals respond only when they see a threshold number of individuals perform a particular behavior. Here, we investigate the role of such "quorum responses" in the movement decisions of fish (three-spine stickleback, Gasterosteus aculeatus). We show that a quorum response to conspecifics can explain how sticklebacks make collective movement decisions, both in the absence and presence of a potential predation risk. Importantly our experimental work shows that a quorum response can reduce the likelihood of amplification of nonadaptive following behavior. Whereas the traveling direction of solitary fish was strongly influenced by a single replica conspecific, the replica was largely ignored by larger groups of four or eight sticklebacks under risk, and the addition of a second replica was required to exert influence on the movement decisions of such groups. Model simulations further predict that quorum responses by fish improve the accuracy and speed of their decision-making over that of independent decision-makers or those using a weak linear response. This study shows that effective and accurate information transfer in groups may be gained only through nonlinear responses of group members to each other, thus highlighting the importance of quorum decision-making. PMID:18474860

  3. Tactile information transfer: A comparison of two stimulation sites

    NASA Astrophysics Data System (ADS)

    Summers, Ian R.; Whybrow, Jon J.; Gratton, Denise A.; Milnes, Peter; Brown, Brian H.; Stevens, John C.

    2005-10-01

    Two experiments on the discrimination of time-varying tactile stimuli were performed, with comparison of stimulus delivery to the distal pad of the right index finger and to the right wrist (palmar surface). Subjects were required to perceive differences in short sequences of computer-generated stimulus elements (experiment 1) or differences in short tactile stimuli derived from a speech signal (experiment 2). The pulse-train stimuli were distinguished by differences in frequency (i.e., pulse repetition rate) and amplitude, and by the presence/absence of gaps (~100-ms duration). Stimulation levels were 10 dB higher at the wrist than at the fingertip, to compensate for the lower vibration sensitivity at the wrist. Results indicate similar gap detection at wrist and fingertip and similar perception of frequency differences. However, perception of amplitude differences was found to be better at the wrist than at the fingertip. Maximum information transfer rates for the stimuli in experiment 1 were estimated at 7 bits s-1 at the wrist and 5 bits s-1 at the fingertip.

  4. Using multiple perspectives to suppress information and complexity

    SciTech Connect

    Kelsey, R.L. |; Webster, R.B.; Hartley, R.T.

    1998-09-01

    Dissemination of battlespace information involves getting information to particular warfighters that is both useful and in a form that facilitates the tasks of those particular warfighters. There are two issues which motivate this problem of dissemination. The first issue deals with disseminating pertinent information to a particular warfighter. This can be thought of as information suppression. The second issue deals with facilitating the use of the information by tailoring the computer interface to the specific tasks of an individual warfighter. This can be thought of as interface complexity suppression. This paper presents a framework for suppressing information using an object-based knowledge representation methodology. This methodology has the ability to represent knowledge and information in multiple perspectives. Information can be suppressed by creating a perspective specific to an individual warfighter. In this way, only the information pertinent and useful to a warfighter is made available to that warfighter. Information is not removed, lost, or changed, but spread among multiple perspectives. Interface complexity is managed in a similar manner. Rather than have one generalized computer interface to access all information, the computer interface can be divided into interface elements. Interface elements can then be selected and arranged into a perspective-specific interface. This is done in a manner to facilitate completion of tasks contained in that perspective. A basic battlespace domain containing ground and air elements and associated warfighters is used to exercise the methodology.

  5. Acoustic radiation force expressed using complex phase shifts and momentum-transfer cross sections.

    PubMed

    Zhang, Likun; Marston, Philip L

    2016-08-01

    Acoustic radiation force is expressed using complex phase shifts of partial wave scattering functions and the momentum-transfer cross section, herein incorporated into acoustics from quantum mechanisms. Imaginary parts of the phase shifts represent dissipation in the object and/or in the boundary layer adjacent to the object. The formula simplifies the force as summation of functions of complex phase shifts of adjacent partial waves involving differences of real parts and sums of imaginary parts, providing an efficient way of exploring the force parameter-space. The formula for the force is proportional to a generalized momentum-transfer cross section for plane waves and no dissipation. PMID:27586777

  6. Entanglement generation and quantum information transfer between spatially-separated qubits in different cavities

    NASA Astrophysics Data System (ADS)

    Yang, Chui-Ping; Su, Qi-Ping; Nori, Franco

    2013-11-01

    The generation and control of quantum states of spatially-separated qubits distributed in different cavities constitute fundamental tasks in cavity quantum electrodynamics (QED). An interesting question in this context is how to prepare entanglement and realize quantum information transfer between qubits located at different cavities, which are important in large-scale quantum information processing. In this paper, we consider a physical system consisting of two cavities and three qubits. Two of the qubits are placed in two different cavities while the remaining one acts as a coupler, which is used to connect the two cavities. We propose an approach for generating quantum entanglement and implementing quantum information transfer between the two spatially-separated inter-cavity qubits. The quantum operations involved in this proposal are performed by a virtual photon process; thus the cavity decay is greatly suppressed during operations. In addition, to complete these tasks, only one coupler qubit and one operation step are needed. Moreover, there is no need to apply classical pulses, so that the engineering complexity is much reduced and the operation procedure is greatly simplified. Finally, our numerical results illustrate that high-fidelity implementation of this proposal using superconducting phase qubits and one-dimensional transmission line resonators is feasible for current circuit QED implementations. This proposal can also be applied to other types of superconducting qubits, including flux and charge qubits.

  7. Surface complexation reaction for phase transfer of hydrophobic quantum dot from nonpolar to polar medium.

    PubMed

    Bhandari, Satyapriya; Roy, Shilaj; Pramanik, Sabyasachi; Chattopadhyay, Arun

    2014-09-01

    Chemical reaction between oleate-capped Zn(x)Cd(1-x)S quantum dots (Qdots) and 8-hydroxyquinoline (HQ) led to formation of a surface complex, which was accompanied by transfer of hydrophobic Qdots from nonpolar (hexane) to polar (water) medium with high efficiency. The stability of the complex on the surface was achieved via involvement of dangling sulfide bonds. Moreover, the transferred hydrophilic Qdots--herein called as quantum dot complex (QDC)--exhibited new and superior optical properties in comparison to bare inorganic complexes with retention of the dimension and core structure of the Qdots. Finally, the new and superior optical properties of water-soluble QDC make them potentially useful for biological--in addition to light emitting device (LED)--applications. PMID:25133937

  8. Ultrafast Spectroscopic Signatures of Coherent Electron-Transfer Mechanisms in a Transition Metal Complex.

    PubMed

    Guo, Zhenkun; Giokas, Paul G; Cheshire, Thomas P; Williams, Olivia F; Dirkes, David J; You, Wei; Moran, Andrew M

    2016-07-28

    The prevalence of ultrafast electron-transfer processes in light-harvesting materials has motivated a deeper understanding of coherent reaction mechanisms. Kinetic models based on the traditional (equilibrium) form of Fermi's Golden Rule are commonly employed to understand photoinduced electron-transfer dynamics. These models fail in two ways when the electron-transfer process is fast compared to solvation dynamics and vibrational dephasing. First, electron-transfer dynamics may be accelerated if the photoexcited wavepacket traverses the point of degeneracy between donor and acceptor states in the solvent coordinate. Second, traditional kinetic models fail to describe electron-transfer transitions that yield products which undergo coherent nuclear motions. We address the second point in this work. Transient absorption spectroscopy and a numerical model are used to investigate coherent back-electron-transfer mechanisms in a transition metal complex composed of titanium and catechol, [Ti(cat)3](2-). The transient absorption experiments reveal coherent wavepacket motions initiated by the back-electron-transfer process. Model calculations suggest that the vibrationally coherent product states may originate in either vibrational populations or coherences of the reactant. That is, vibrational coherence may be produced even if the reactant does not undergo coherent nuclear motions. The analysis raises a question of broader significance: can a vibrational population-to-coherence transition (i.e., a nonsecular transition) accelerate electron-transfer reactions even when the rate is slower than vibrational dephasing? PMID:27362388

  9. Electron transfer from flavin to iron in the Pseudomonas oleovorans rubredoxin reductase-rubredoxin electron transfer complex.

    PubMed

    Lee, H J; Basran, J; Scrutton, N S

    1998-11-01

    Rubredoxin reductase (RR) and rubredoxin form a soluble and physiological eT complex. The complex provides reducing equivalents for a membrane-bound omega-hydroxylase, required for the hydroxylation of alkanes and related compounds. The gene (alkT) encoding RR has been overexpressed and the enzyme purified in amounts suitable for studies of eT by stopped-flow spectroscopy. The eT reactions from NADH to the flavin of RR and from reduced RR to the 1Fe and 2Fe forms of rubredoxin have been characterized by transient kinetic and thermodynamic analysis. The reductive half-reaction proceeds in a one-step reaction involving oxidized enzyme and a two-electron-reduced enzyme-NAD+ charge-transfer complex. Flavin reduction is observed at 450 nm and charge-transfer formation at 750 nm; both steps are hyperbolically dependent on NADH concentration. The limiting flavin reduction rate (180 +/- 4 s-1) is comparable to the limiting rate for charge-transfer formation (189 +/- 7 s-1) and analysis at 450 and 750 nm yielded enzyme-NADH dissociation constants of 36 +/- 2 and 43 +/- 5 microM, respectively. Thermodynamic analysis of the reductive half-reaction yielded values for changes in entropy (DeltaS = -65.8 +/- 2.2 J mol-1 K-1), enthalpy (DeltaH = 37.8 +/- 0.6 kJ mol-1) and Gibbs free energy (DeltaG = 57.5 +/- 0.7 kJ mol-1 at 298 K) during hydride ion transfer to the flavin N5 atom. Spectral analysis of mixtures of 1Fe or 2Fe rubredoxin and RR suggest that conformational changes accompany eT complex assembly. Both the 1Fe (nonphysiological) and 2Fe (physiological) forms of rubredoxin were found to oxidize two electron-reduced rubredoxin reductase with approximately equal facility. Rates for the reduction of rubredoxin are hyperbolically dependent on rubredoxin concentration and the limiting rates are 72. 7 +/- 0.6 and 55.2 +/- 0.3 s-1 for the 1Fe and 2Fe forms, respectively. Analysis of the temperature dependence of eT to rubredoxin using eT theory revealed that the reaction is not

  10. Nitrene Metathesis and Catalytic Nitrene Transfer Promoted by Niobium Bis(imido) Complexes.

    PubMed

    Kriegel, Benjamin M; Bergman, Robert G; Arnold, John

    2016-01-13

    We report a metathesis reaction in which a nitrene fragment from an isocyanide ligand is exchanged with a nitrene fragment of an imido ligand in a series of niobium bis(imido) complexes. One of these bis(imido) complexes also promotes nitrene transfer to catalytically generate asymmetric dialkylcarbodiimides from azides and isocyanides in a process involving the Nb(V)/Nb(III) redox couple. PMID:26698833

  11. Writing information transfers for out-of-hours palliative care: a controlled trial among GPs

    PubMed Central

    Schweitzer, Bart; Blankenstein, Nettie; Slort, Willemjan; Knol, Dirk L.; Deliens, Luc; Van Der Horst, Henriette

    2016-01-01

    Objective The aim was to evaluate the effect of the implementation of an information handover form regarding patients receiving palliative care. Outcome was the information available for the out-of-hours GP co-operative. Design We conducted a controlled trial. Setting All GPs in Amsterdam, The Netherlands. Intervention The experimental group (N = 240) received an information handover form and an invitation for a one-hour training, the control group (N =  186) did not receive a handover form or training. We studied contacts with the GP co-operative concerning patients in palliative care for the presence and quality of information transferred by the patient's own GP. Main outcome measures Proportion of contacts in which information was available and proportion of adequate information transfer. Results. Overall information was transferred by the GPs in 179 of the 772 first palliative contacts (23.2%). The number of contacts in the experimental group in which information was available increased significantly after intervention from 21% to 30%, compared to a decrease from 23% to 19% in the control group. The training had no additional effect. The content of the transferred information was adequate in 61.5%. There was no significant difference in the quality of the content between the groups. Conclusion The introduction of a handover form resulted in a moderate increase of information transfers to the GP co-operative. However, the total percentage of contacts in which this information was present remained rather low. GP co-operatives should develop additional policies to improve information transfer. Key points The out-of-hours period is potentially problematic for the delivery of optimal palliative care, often due to inadequate information transfer. Introduction of a handover form resulted in a moderate increase of transferred information. The percentage of palliative contacts remained low in cases where information was available. Adequate information

  12. In Situ Catalyst Modification in Atom Transfer Radical Reactions with Ruthenium Benzylidene Complexes.

    PubMed

    Lee, Juneyoung; Grandner, Jessica M; Engle, Keary M; Houk, K N; Grubbs, Robert H

    2016-06-01

    Ruthenium benzylidene complexes are well-known as olefin metathesis catalysts. Several reports have demonstrated the ability of these catalysts to also facilitate atom transfer radical (ATR) reactions, such as atom transfer radical addition (ATRA) and atom transfer radical polymerization (ATRP). However, while the mechanism of olefin metathesis with ruthenium benzylidenes has been well-studied, the mechanism by which ruthenium benzylidenes promote ATR reactions remains unknown. To probe this question, we have analyzed seven different ruthenium benzylidene complexes for ATR reactivity. Kinetic studies by (1)H NMR revealed that ruthenium benzylidene complexes are rapidly converted into new ATRA-active, metathesis-inactive species under typical ATRA conditions. When ruthenium benzylidene complexes were activated prior to substrate addition, the resulting activated species exhibited enhanced kinetic reactivity in ATRA with no significant difference in overall product yield compared to the original complexes. Even at low temperature, where the original intact complexes did not catalyze the reaction, preactivated catalysts successfully reacted. Only the ruthenium benzylidene complexes that could be rapidly transformed into ATRA-active species could successfully catalyze ATRP, whereas other complexes preferred redox-initiated free radical polymerization. Kinetic measurements along with additional mechanistic and computational studies show that a metathesis-inactive ruthenium species, generated in situ from the ruthenium benzylidene complexes, is the active catalyst in ATR reactions. Based on data from (1) H, (13)C, and (31)P NMR spectroscopy and X-ray crystallography, we suspect that this ATRA-active species is a RuxCly(PCy3)z complex. PMID:27186790

  13. Controlling energy transfer in ytterbium complexes: oxygen dependent lanthanide luminescence and singlet oxygen formation.

    PubMed

    Watkis, Andrew; Hueting, Rebekka; Sørensen, Thomas Just; Tropiano, Manuel; Faulkner, Stephen

    2015-11-01

    Pyrene-appended ytterbium complexes have been prepared using Ugi reactions to vary the chromophore-lanthanide separation. Formation of the ytterbium(iii) excited state is sensitised via both the singlet and triplet excited states of the chromophore. Energy transfer from the latter is relatively slow, and gives rise to oxygen-dependent luminescence. PMID:26346499

  14. Solvent-induced reversible solid-state colour change of an intramolecular charge-transfer complex.

    PubMed

    Li, Ping; Maier, Josef M; Hwang, Jungwun; Smith, Mark D; Krause, Jeanette A; Mullis, Brian T; Strickland, Sharon M S; Shimizu, Ken D

    2015-10-11

    A dynamic intramolecular charge-transfer (CT) complex was designed that displayed reversible colour changes in the solid-state when treated with different organic solvents. The origins of the dichromatism were shown to be due to solvent-inclusion, which induced changes in the relative orientations of the donor pyrene and acceptor naphthalenediimide units. PMID:26299357

  15. Enhanced fluorescent resonant energy transfer of DNA conjugates complexed with surfactants and divalent metal ions.

    PubMed

    Oh, Taeseok; Choi, Jae-Young; Heller, Michael J

    2016-04-21

    Dimerization and resultant quenching of donor and acceptor dyes conjugated on DNA causes loss of fluorescent resonant energy transfer (FRET) efficiency. However, when complexed with surfactants and divalent metal ions, sheathing effects insulate and shield the DNA structures, reducing dimerization and quenching which leads to significant enhancement of FRET efficiency. PMID:26985458

  16. Electronic coherence and the kinetics of inter-complex energy transfer in light-harvesting systems.

    PubMed

    Huo, Pengfei; Miller, Thomas F

    2015-12-14

    We apply real-time path-integral dynamics simulations to characterize the role of electronic coherence in inter-complex excitation energy transfer (EET) processes. The analysis is performed using a system-bath model that exhibits the essential features of light-harvesting networks, including strong intra-complex electronic coupling and weak inter-complex coupling. Strong intra-complex coupling is known to generate both static and dynamic electron coherences, which delocalize the exciton over multiple chromophores and potentially influence the inter-complex EET dynamics. With numerical results from partial linearized density matrix (PLDM) real-time path-integral calculations, it is found that both static and dynamic coherence are correlated with the rate of inter-complex EET. To distinguish the impact of these two types of intra-complex coherence on the rate of inter-complex EET, we use Multi-Chromophore Förster Resonance Energy Transfer (MC-FRET) theory to map the original parameterization of the system-bath model to an alternative parameterization for which the effects of static coherence are preserved while the effects of dynamic coherence are largely eliminated. It is then shown that both parameterizations of the model (i.e., the original that supports dynamic coherence and the alternative that eliminates it), exhibit nearly identical EET kinetics and population dynamics over a wide range of parameters. These observations are found to hold for cases in which either the EET donor or acceptor is a dimeric complex and for cases in which the dimeric complex is either symmetric or asymmetric. The results from this study suggest that dynamic coherence plays only a minor role in the actual kinetics of inter-complex EET, whereas static coherence largely governs the kinetics of incoherent inter-complex EET in light-harvesting networks. PMID:26073739

  17. Nonphotochemical Hole-Burning Studies of Energy Transfer Dynamics in Antenna Complexes of Photosynthetic Bacteria

    SciTech Connect

    Satoshi Matsuzaki

    2002-06-27

    This thesis contains the candidate's original work on excitonic structure and energy transfer dynamics of two bacterial antenna complexes as studied using spectral hole-burning spectroscopy. The general introduction is divided into two chapters (1 and 2). Chapter 1 provides background material on photosynthesis and bacterial antenna complexes with emphasis on the two bacterial antenna systems related to the thesis research. Chapter 2 reviews the underlying principles and mechanism of persistent nonphotochemical hole-burning (NPHB) spectroscopy. Relevant energy transfer theories are also discussed. Chapters 3 and 4 are papers by the candidate that have been published. Chapter 3 describes the application of NPHB spectroscopy to the Fenna-Matthews-Olson (FMO) complex from the green sulfur bacterium Prosthecochloris aestuarii; emphasis is on determination of the low energy vibrational structure that is important for understanding the energy transfer process associated within three lowest energy Q{sub y}-states of the complex. The results are compared with those obtained earlier on the FMO complex from Chlorobium tepidum. In Chapter 4, the energy transfer dynamics of the B800 molecules of intact LH2 and B800-deficient LH2 complexes of the purple bacterium Rhodopseudomonas acidophila are compared. New insights on the additional decay channel of the B800 ring of bacteriochlorophyll{sub a} (BChl{sub a}) molecules are provided. General conclusions are given in Chapter 5. A version of the hole spectrum simulation program written by the candidate for the FMO complex study (Chapter 3) is included as an appendix. The references for each chapter are given at the end of each chapter.

  18. The free-energy barrier to hydride transfer across a dipalladium complex.

    PubMed

    Vanston, C R; Kearley, G J; Edwards, A J; Darwish, T A; de Souza, N R; Ramirez-Cuesta, A J; Gardiner, M G

    2015-01-01

    We use density-functional theory molecular dynamics (DFT-MD) simulations to determine the hydride transfer coordinate between palladium centres of the crystallographically observed terminal hydride locations, Pd-Pd-H, originally postulated for the solution dynamics of the complex bis-NHC dipalladium hydride [{(MesIm)2CH2}2Pd2H][PF6], and then calculate the free-energy along this coordinate. We estimate the transfer barrier-height to be about 20 kcal mol(-1) with a hydride transfer rate in the order of seconds at room temperature. We validate our DFT-MD modelling using inelastic neutron scattering which reveals anharmonicity of the hydride environment that is so pronounced that there is complete failure of the harmonic model for the hydride ligand. The simulations are extended to high temperature to bring the H-transfer to a rate that is accessible to the simulation technique. PMID:25652724

  19. Review: Formation of Peptide Radical Ions Through Dissociative Electron Transfer in Ternary Metal-Ligand-Peptide Complexes

    SciTech Connect

    Chu, Ivan K.; Laskin, Julia

    2011-12-31

    The formation and fragmentation of odd-electron ions of peptides and proteins is of interest to applications in biological mass spectrometry. Gas-phase redox chemistry occurring during collision-induced dissociation of ternary metal-ligand-peptide complexes enables the formation of a variety of peptide radicals including the canonical radical cations, M{sup +{sm_bullet}}, radical dications, [M{sup +}H]{sup 2+{sm_bullet}}, radical anions, [M-2H]{sup -{sm_bullet}}. In addition, odd-electron peptide ions with well-defined initial location of the radical site are produced through side chain losses from the radical ions. Subsequent fragmentation of these species provides information on the role of charge and the location of the radical site on the competition between radical-induced and proton-driven fragmentation of odd-electron peptide ions. This account summarizes current understanding of the factors that control the efficiency of the intramolecular electron transfer (ET) in ternary metal-ligand-peptide complexes resulting in formation of odd-electron peptide ions. Specifically, we discuss the effect of the metal center, the ligand and the peptide structure on the competition between the ET, proton transfer (PT), and loss of neutral peptide and neutral peptide fragments from the complex. Fundamental studies of the structures, stabilities, and the energetics and dynamics of fragmentation of such complexes are also important for detailed molecular-level understanding of photosynthesis and respiration in biological systems.

  20. 76 FR 2758 - Agency Information Collection (Evidence for Transfer of Entitlement of Education Benefits (CFR 21...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-01-14

    ... AFFAIRS Agency Information Collection (Evidence for Transfer of Entitlement of Education Benefits (CFR 21... refer to ``OMB Control No. 2900-0708.'' SUPPLEMENTARY INFORMATION: Title: Evidence for Transfer of... children, or a combination of the spouse and children. VA will accept DOD Form 2366-1 as evidence that...

  1. Informal Learning and the Transfer of Learning: How Managers Develop Proficiency

    ERIC Educational Resources Information Center

    Enos, Michael D.; Kehrhahn, Marijke Thamm; Bell, Alexandra

    2003-01-01

    This study examined how the extent to which managers engaged in informal learning, perceptions of support in the transfer environment, and level of managerial proficiency related to transfer of learning in twenty core managerial skills. The results suggested that informal learning is predominantly a social process and that managers with high…

  2. 77 FR 57105 - Notice of Proposed Information Collection: Comment Request; Application for the Transfer of...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-09-17

    ... URBAN DEVELOPMENT Notice of Proposed Information Collection: Comment Request; Application for the Transfer of Physical Assets AGENCY: Office of the Assistant Secretary for Housing, HUD. ACTION: Notice.... This Notice also lists the following information: Title of Proposal: Application for the Transfer...

  3. Probing excited state charge transfer dynamics in a heteroleptic ruthenium complex.

    PubMed

    Ghosh, Rajib; Palit, Dipak K

    2014-01-01

    Dynamics of metal to ligand charge transfer in the excited states of ruthenium polypyridyl complexes, which have shown promise as materials for artificial solar energy harvesting, has been of immense interest recently. Mixed ligand complexes are especially important for broader absorption in the visible region. Dynamics of ultrafast vibrational energy relaxation and inter-ligand charge transfer processes in the excited states of a heteroleptic ruthenium complex, [Ru(bpy)2(pap)](ClO4)2 (where bpy is 2,2'-bipyridine and pap is 2-(phenylazo)pyridine) have been investigated using femtosecond to nanosecond time-resolved transient absorption spectroscopic techniques. A good agreement between the TA spectrum of the lowest excited (3)MLCT state of [Ru(bpy)2(pap)](ClO4)2 complex and the anion radical spectrum of the pap ligand, which has been generated using the pulse radiolysis technique, confirmed the charge localization at the pap ligand. While the lifetime of the inter-ligand charge transfer from the bpy to the pap ligand in the (3)MLCT state is about 2.5 ps, vibrational cooling of the pap-localized(3)MLCT state occurs over a much longer time scale with a lifetime of about 35 ps. Ultrafast charge localization dynamics observed here may have important consequences in artificial solar energy harvesting systems, which employ heteroleptic ruthenium complexes. PMID:24247908

  4. Electron transfer reactions of osmium(II) complexes with phenols and phenolic acids

    NASA Astrophysics Data System (ADS)

    Rajeswari, Angusamy; Ramdass, Arumugam; Muthu Mareeswaran, Paulpandian; Velayudham, Murugesan; Rajagopal, Seenivasan

    2016-07-01

    Three [Os(NN)3]2+ complexes (NN = polypyridine) with ligands of varying hydrophobicity were synthesized and characterized by NMR spectral techniques. The geometry of the molecules are optimized by DFT calculations. The interaction between [Os(NN)3]2+ complexes and phenolate ion in ground state is confirmed by absorption spectral study and the binding constant values are in the range of 3-740 M-1. The photoinduced electron transfer reaction of these [Os(NN)3]2+ complexes with phenols and phenolic acids at pH 12.5 leads to the formation of phenoxyl radical confirmed through transient absorption spectral study. Binding constants and electron transfer rate constants within the [Os(NN)3]2+-phenolate ion adduct account for the change for the overall quenching constant with the change of structure of reactants.

  5. Synthesis and spectroscopic studies of the charge transfer complexes of 2- and 3-aminopyridine

    NASA Astrophysics Data System (ADS)

    Mostafa, Adel; Bazzi, Hassan S.

    2009-09-01

    The interactions of the electron donors 2-aminopyridine (2APY) and 3-aminopyridine (3APY) with the π-acceptors tetracyanoethylene (TCNE), 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ), 2-chloro-1,3,5-trinitrobenzene (picryl chloride, PC), and 2,3,5,6-tetrachloro-1,4-benzoquinone (chloranil) were studied spectrophotometrically in chloroform at room temperature. The electronic and infrared spectra of the formed molecular charge transfer (CT) complexes were recorded. Photometric titration showed that the stoichiometries of the reactions were fixed and depended on the nature of both the donor and the acceptor. The molecular structures of the CT-complexes were, however, independent of the position of the amino group on the pyridine ring and were formulated as [(APY)(TCNE)], [(APY)(DDQ)], [(APY)(PC)], and [(APY) (chloranil)]. The formation constants ( KCT), charge transfer energy ( ECT) and molar extinction coefficients ( ɛCT) of the formed CT-complexes were obtained.

  6. Dynamics of rumor-like information dissemination in complex networks

    NASA Astrophysics Data System (ADS)

    Nekovee, Maziar; Moreno, Yamir; Bianconi, Ginestra

    2005-03-01

    An important dynamic process that takes place in complex networks is the spreading of information via rumor-like mechanisms. In addition to their relevance to propagation of rumors and fads in human society, such mechanism are also the basis of an important class of collective communication protocols in complex computer networks, such as the Internet and the peer-to-peer systems. In this talk we present results of our analytical, numerical and large-scale Monte Carlo simulation studies of this process on several classes of complex networks, including random graphs, scale-free networks, and random and small-world topological graphs. Our studies point out to important differences between the dynamics of rumor spreading and that of virus spreading in such networks, and provide new insights into the complex interplay between the spreading phenomena and network topology.

  7. Energy transfer and clustering of photosynthetic light-harvesting complexes in reconstituted lipid membranes

    NASA Astrophysics Data System (ADS)

    Dewa, Takehisa; Sumino, Ayumi; Watanabe, Natsuko; Noji, Tomoyasu; Nango, Mamoru

    2013-06-01

    In purple photosynthetic bacteria, light-harvesting complex 2 (LH2) and light harvesting/reaction centre core complex (LH1-RC) play the key roles of capturing and transferring light energy and subsequent charge separation. These photosynthetic apparatuses form a supramolecular assembly; however, how the assembly influences the efficiency of energy conversion is not yet clear. We addressed this issue by evaluating the energy transfer in reconstituted photosynthetic protein complexes LH2 and LH1-RC and studying the structures and the membrane environment of the LH2/LH1-RC assemblies, which had been embedded into various lipid bilayers. Thus, LH2 and LH1-RC from Rhodopseudomonas palustris 2.1.6 were reconstituted in phosphatidylglycerol (PG), phosphatidylcholine (PC), and phosphatidylethanolamine (PE)/PG/cardiolipin (CL). Efficient energy transfer from LH2 to LH1-RC was observed in the PC and PE/PG/CL membranes. Atomic force microscopy revealed that LH2 and LH1-RC were heterogeneously distributed to form clusters in the PC and PE/PG/CL membranes. The results indicated that the phospholipid species influenced the cluster formation of LH2 and LH1-RC as well as the energy transfer efficiency.

  8. 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

  9. 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

  10. High pressure study of charge transfer complexes and radical ion salts: A review

    NASA Astrophysics Data System (ADS)

    Singh, Yadunath

    2016-05-01

    High pressure is an important tool to study of material in respect of variation in interatomic distances, phase transitions and other physical properties. The pressure study of charge transfer complexes and radical ion salts provide us a better understanding about the effect of charge transfer forces, structural changes, formation of new ground states, suppression ofPeierls distortions occurs particularly at low temperatures and the intra-molecular overlapping etc. in these materials. The pressure plays a significant role in bringing superconducting transitions in the organic materials.

  11. Theoretical Investigation of OCN(-) Charge Transfer Complexes in Condensed Phase Media: Spectroscopic Properties in Amorphous Ice

    NASA Technical Reports Server (NTRS)

    Park, Jin-Young; Woon, David E.

    2004-01-01

    Density functional theory (DFT) calculations of cyanate (OCN(-)) charge-transfer complexes were performed to model the "XCN" feature observed in interstellar icy grain mantles. OCN(-) charge-transfer complexes were formed from precursor combinations of HNCO or HOCN with either NH3 or H2O. Three different solvation strategies for realistically modeling the ice matrix environment were explored, including (1) continuum solvation, (2) pure DFT cluster calculations, and (3) an ONIOM DFT/PM3 cluster calculation. The model complexes were evaluated by their ability to reproduce seven spectroscopic measurements associated with XCN: the band origin of the OCN(-) asymmetric stretching mode, shifts in that frequency due to isotopic substitutions of C, N, O, and H, plus two weak features. The continuum solvent field method produced results consistent with some of the experimental data but failed to account for other behavior due to its limited capacity to describe molecular interactions with solvent. DFT cluster calculations successfully reproduced the available spectroscopic measurements very well. In particular, the deuterium shift showed excellent agreement in complexes where OCN(-) was fully solvated. Detailed studies of representative complexes including from two to twelve water molecules allowed the exploration of various possible solvation structures and provided insights into solvation trends. Moreover, complexes arising from cyanic or isocyanic acid in pure water suggested an alternative mechanism for the formation of OCN(-) charge-transfer complexes without the need for a strong base such as NH3 to be present. An extended ONIOM (B3LYP/PM3) cluster calculation was also performed to assess the impact of a more realistic environment on HNCO dissociation in pure water.

  12. Information, Cooperation, and the Blurring of Boundaries--Technology Transfer in German and American Discourses

    ERIC Educational Resources Information Center

    Krucken, Georg; Meier, Frank; Muller, Andre

    2007-01-01

    The aim of this paper is to examine changing discursive conceptualizations of technology transfer mechanisms for speeding up innovation in Germany and the US since World War II with particular emphasis on universities. According to our analysis, the concepts of technology transfer are getting more and more complex, taking off from a linear model…

  13. Extensive Charge Reduction and Dissociation of Intact Protein Complexes Following Electron Transfer on a Quadrupole-Ion Mobility-Time-of-Flight MS

    NASA Astrophysics Data System (ADS)

    Lermyte, Frederik; Williams, Jonathan P.; Brown, Jeffery M.; Martin, Esther M.; Sobott, Frank

    2015-07-01

    Non-dissociative charge reduction, typically considered to be an unwanted side reaction in electron transfer dissociation (ETD) experiments, can be enhanced significantly in order to reduce the charge state of intact protein complexes to as low as 1+ on a commercially available Q-IM-TOF instrument. This allows for the detection of large complexes beyond 100,000 m/z, while at the same time generating top-down ETD fragments, which provide sequence information from surface-exposed parts of the folded structure. Optimization of the supplemental activation has proven to be crucial in these experiments and the charge-reduced species are most likely the product of both proton transfer (PTR) and non-dissociative electron transfer (ETnoD) reactions that occur prior to the ion mobility cell. Applications of this approach range from deconvolution of complex spectra to the manipulation of charge states of gas-phase ions.

  14. Influence of Humic Acid Complexation with Metal Ions on Extracellular Electron Transfer Activity.

    PubMed

    Zhou, Shungui; Chen, Shanshan; Yuan, Yong; Lu, Qin

    2015-01-01

    Humic acids (HAs) can act as electron shuttles and mediate biogeochemical cycles, thereby influencing the transformation of nutrients and environmental pollutants. HAs commonly complex with metals in the environment, but few studies have focused on how these metals affect the roles of HAs in extracellular electron transfer (EET). In this study, HA-metal (HA-M) complexes (HA-Fe, HA-Cu, and HA-Al) were prepared and characterized. The electron shuttle capacities of HA-M complexes were experimentally evaluated through microbial Fe(III) reduction, biocurrent generation, and microbial azoreduction. The results show that the electron shuttle capacities of HAs were enhanced after complexation with Fe but were weakened when using Cu or Al. Density functional theory calculations were performed to explore the structural geometry of the HA-M complexes and revealed the best binding sites of the HAs to metals and the varied charge transfer rate constants (k). The EET activity of the HA-M complexes were in the order HA-Fe > HA-Cu > HA-Al. These findings have important implications for biogeochemical redox processes given the ubiquitous nature of both HAs and various metals in the environment. PMID:26593782

  15. Ruthenium(ii) complexes of hemilabile pincer ligands: synthesis and catalysing the transfer hydrogenation of ketones.

    PubMed

    Nair, Ashwin G; McBurney, Roy T; Walker, D Barney; Page, Michael J; Gatus, Mark R D; Bhadbhade, Mohan; Messerle, Barbara A

    2016-09-28

    A series of Ru(ii) complexes were synthesised based on a hemilabile pyrazole-N-heterocyclic carbene (NHC)-pyrazole (C3N2H3)CH2(C3N2H2)CH2(C3N2H3) NCN pincer ligand 1. All complexes were fully characterised using single crystal X-ray crystallography and multinuclear NMR spectroscopy. Hemilabile ligands provide flexible coordination modes for the coordinating metal ion which can play a significant effect on the efficiency and mechanism of catalysis by the resulting complex. Here we observed and isolated mono-, bi- and tri-dentate complexes of both Ag(i) and Ru(ii) with 1 in which the resultant coordination mode was controlled by careful reagent selection. The catalytic activity of the Ru(ii) complexes for the transfer hydrogenation reaction of acetophenone with isopropanol was investigated. The unexpected formation of the pentaborate anion, [B5O6(OH)4](-), during the synthesis of complex 6a was found to have an unexpected positive effect by enhancing the catalysis rate. This work provides insights into the roles that different coordination modes, counterions and ligand hemilability play on the catalytic activity in transfer hydrogenations. PMID:27539740

  16. Influence of Humic Acid Complexation with Metal Ions on Extracellular Electron Transfer Activity

    PubMed Central

    Zhou, Shungui; Chen, Shanshan; Yuan, Yong; Lu, Qin

    2015-01-01

    Humic acids (HAs) can act as electron shuttles and mediate biogeochemical cycles, thereby influencing the transformation of nutrients and environmental pollutants. HAs commonly complex with metals in the environment, but few studies have focused on how these metals affect the roles of HAs in extracellular electron transfer (EET). In this study, HA-metal (HA-M) complexes (HA-Fe, HA-Cu, and HA-Al) were prepared and characterized. The electron shuttle capacities of HA-M complexes were experimentally evaluated through microbial Fe(III) reduction, biocurrent generation, and microbial azoreduction. The results show that the electron shuttle capacities of HAs were enhanced after complexation with Fe but were weakened when using Cu or Al. Density functional theory calculations were performed to explore the structural geometry of the HA-M complexes and revealed the best binding sites of the HAs to metals and the varied charge transfer rate constants (k). The EET activity of the HA-M complexes were in the order HA-Fe > HA-Cu > HA-Al. These findings have important implications for biogeochemical redox processes given the ubiquitous nature of both HAs and various metals in the environment. PMID:26593782

  17. Influence of Humic Acid Complexation with Metal Ions on Extracellular Electron Transfer Activity

    NASA Astrophysics Data System (ADS)

    Zhou, Shungui; Chen, Shanshan; Yuan, Yong; Lu, Qin

    2015-11-01

    Humic acids (HAs) can act as electron shuttles and mediate biogeochemical cycles, thereby influencing the transformation of nutrients and environmental pollutants. HAs commonly complex with metals in the environment, but few studies have focused on how these metals affect the roles of HAs in extracellular electron transfer (EET). In this study, HA-metal (HA-M) complexes (HA-Fe, HA-Cu, and HA-Al) were prepared and characterized. The electron shuttle capacities of HA-M complexes were experimentally evaluated through microbial Fe(III) reduction, biocurrent generation, and microbial azoreduction. The results show that the electron shuttle capacities of HAs were enhanced after complexation with Fe but were weakened when using Cu or Al. Density functional theory calculations were performed to explore the structural geometry of the HA-M complexes and revealed the best binding sites of the HAs to metals and the varied charge transfer rate constants (k). The EET activity of the HA-M complexes were in the order HA-Fe > HA-Cu > HA-Al. These findings have important implications for biogeochemical redox processes given the ubiquitous nature of both HAs and various metals in the environment.

  18. 49 CFR 8.23 - Classified information transferred to the Department of Transportation.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 49 Transportation 1 2010-10-01 2010-10-01 false Classified information transferred to the Department of Transportation. 8.23 Section 8.23 Transportation Office of the Secretary of Transportation CLASSIFIED INFORMATION: CLASSIFICATION/DECLASSIFICATION/ACCESS Classification/Declassification of Information § 8.23 Classified information...

  19. 49 CFR 8.23 - Classified information transferred to the Department of Transportation.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 49 Transportation 1 2011-10-01 2011-10-01 false Classified information transferred to the Department of Transportation. 8.23 Section 8.23 Transportation Office of the Secretary of Transportation CLASSIFIED INFORMATION: CLASSIFICATION/DECLASSIFICATION/ACCESS Classification/Declassification of Information § 8.23 Classified information...

  20. 49 CFR 8.23 - Classified information transferred to the Department of Transportation.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 49 Transportation 1 2014-10-01 2014-10-01 false Classified information transferred to the Department of Transportation. 8.23 Section 8.23 Transportation Office of the Secretary of Transportation CLASSIFIED INFORMATION: CLASSIFICATION/DECLASSIFICATION/ACCESS Classification/Declassification of Information § 8.23 Classified information...

  1. 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

  2. Excitation energy transfer in natural photosynthetic complexes and chlorophyll trefoils: hole-burning and single complex/trefoil spectroscopic studies

    SciTech Connect

    Ryszard Jankowiak, Kansas State University, Department of Chemistry, CBC Bldg., Manhattan KS, 66505; Phone: 532-6785

    2012-09-12

    In this project we studied both natural photosynthetic antenna complexes and various artificial systems (e.g. chlorophyll (Chl) trefoils) using high resolution hole-burning (HB) spectroscopy and excitonic calculations. Results obtained provided more insight into the electronic (excitonic) structure, inhomogeneity, electron-phonon coupling strength, vibrational frequencies, and excitation energy (or electron) transfer (EET) processes in several antennas and reaction centers. For example, our recent work provided important constraints and parameters for more advanced excitonic calculations of CP43, CP47, and PSII core complexes. Improved theoretical description of HB spectra for various model systems offers new insight into the excitonic structure and composition of low-energy absorption traps in very several antenna protein complexes and reaction centers. We anticipate that better understanding of HB spectra obtained for various photosynthetic complexes and their simultaneous fits with other optical spectra (i.e. absorption, emission, and circular dichroism spectra) provides more insight into the underlying electronic structures of these important biological systems. Our recent progress provides a necessary framework for probing the electronic structure of these systems via Hole Burning Spectroscopy. For example, we have shown that the theoretical description of non-resonant holes is more restrictive (in terms of possible site energies) than those of absorption and emission spectra. We have demonstrated that simultaneous description of linear optical spectra along with HB spectra provides more realistic site energies. We have also developed new algorithms to describe both nonresonant and resonant hole-burn spectra using more advanced Redfield theory. Simultaneous description of various optical spectra for complex biological system, e.g. artificial antenna systems, FMO protein complexes, water soluble protein complexes, and various mutants of reaction centers

  3. Information processing using a single dynamical node as complex system

    PubMed Central

    Appeltant, L.; Soriano, M.C.; Van der Sande, G.; Danckaert, J.; Massar, S.; Dambre, J.; Schrauwen, B.; Mirasso, C.R.; Fischer, I.

    2011-01-01

    Novel methods for information processing are highly desired in our information-driven society. Inspired by the brain's ability to process information, the recently introduced paradigm known as 'reservoir computing' shows that complex networks can efficiently perform computation. Here we introduce a novel architecture that reduces the usually required large number of elements to a single nonlinear node with delayed feedback. Through an electronic implementation, we experimentally and numerically demonstrate excellent performance in a speech recognition benchmark. Complementary numerical studies also show excellent performance for a time series prediction benchmark. These results prove that delay-dynamical systems, even in their simplest manifestation, can perform efficient information processing. This finding paves the way to feasible and resource-efficient technological implementations of reservoir computing. PMID:21915110

  4. Teaching for Transfer: Reconciling the Framework with Disciplinary Information Literacy

    ERIC Educational Resources Information Center

    Kuglitsch, Rebecca Z.

    2015-01-01

    This article explores the tension between information literacy as a generalizable skill and as a skill within the disciplines. The new ACRL Framework for Information Literacy for Higher Education addresses many challenges facing the previous ACRL Information Literacy Competency Standards for Higher Education, but the tension between disciplinary…

  5. Biological Information Transfer Beyond the Genetic Code: The Sugar Code

    NASA Astrophysics Data System (ADS)

    Gabius, H.-J.

    In the era of genetic engineering, cloning, and genome sequencing the focus of research on the genetic code has received an even further accentuation in the public eye. In attempting, however, to understand intra- and intercellular recognition processes comprehensively, the two biochemical dimensions established by nucleic acids and proteins are not sufficient to satisfactorily explain all molecular events in, for example, cell adhesion or routing. The consideration of further code systems is essential to bridge this gap. A third biochemical alphabet forming code words with an information storage capacity second to no other substance class in rather small units (words, sentences) is established by monosaccharides (letters). As hardware oligosaccharides surpass peptides by more than seven orders of magnitude in the theoretical ability to build isomers, when the total of conceivable hexamers is calculated. In addition to the sequence complexity, the use of magnetic resonance spectroscopy and molecular modeling has been instrumental in discovering that even small glycans can often reside in not only one but several distinct low-energy conformations (keys). Intriguingly, conformers can display notably different capacities to fit snugly into the binding site of nonhomologous receptors (locks). This process, experimentally verified for two classes of lectins, is termed "differential conformer selection." It adds potential for shifts of the conformer equilibrium to modulate ligand properties dynamically and reversibly to the well-known changes in sequence (including anomeric positioning and linkage points) and in pattern of substitution, for example, by sulfation. In the intimate interplay with sugar receptors (lectins, enzymes, and antibodies) the message of coding units of the sugar code is deciphered. Their recognition will trigger postbinding signaling and the intended biological response. Knowledge about the driving forces for the molecular rendezvous, i

  6. Structural insight into the TRIAP1/PRELI-like domain family of mitochondrial phospholipid transfer complexes

    PubMed Central

    Miliara, Xeni; Garnett, James A; Tatsuta, Takashi; Abid Ali, Ferdos; Baldie, Heather; Pérez-Dorado, Inmaculada; Simpson, Peter; Yague, Ernesto; Langer, Thomas; Matthews, Stephen

    2015-01-01

    The composition of the mitochondrial membrane is important for its architecture and proper function. Mitochondria depend on a tightly regulated supply of phospholipid via intra-mitochondrial synthesis and by direct import from the endoplasmic reticulum. The Ups1/PRELI-like family together with its mitochondrial chaperones (TRIAP1/Mdm35) represent a unique heterodimeric lipid transfer system that is evolutionary conserved from yeast to man. Work presented here provides new atomic resolution insight into the function of a human member of this system. Crystal structures of free TRIAP1 and the TRIAP1–SLMO1 complex reveal how the PRELI domain is chaperoned during import into the intermembrane mitochondrial space. The structural resemblance of PRELI-like domain of SLMO1 with that of mammalian phoshatidylinositol transfer proteins (PITPs) suggest that they share similar lipid transfer mechanisms, in which access to a buried phospholipid-binding cavity is regulated by conformationally adaptable loops. PMID:26071602

  7. Structural insight into the TRIAP1/PRELI-like domain family of mitochondrial phospholipid transfer complexes.

    PubMed

    Miliara, Xeni; Garnett, James A; Tatsuta, Takashi; Abid Ali, Ferdos; Baldie, Heather; Pérez-Dorado, Inmaculada; Simpson, Peter; Yague, Ernesto; Langer, Thomas; Matthews, Stephen

    2015-07-01

    The composition of the mitochondrial membrane is important for its architecture and proper function. Mitochondria depend on a tightly regulated supply of phospholipid via intra-mitochondrial synthesis and by direct import from the endoplasmic reticulum. The Ups1/PRELI-like family together with its mitochondrial chaperones (TRIAP1/Mdm35) represent a unique heterodimeric lipid transfer system that is evolutionary conserved from yeast to man. Work presented here provides new atomic resolution insight into the function of a human member of this system. Crystal structures of free TRIAP1 and the TRIAP1-SLMO1 complex reveal how the PRELI domain is chaperoned during import into the intermembrane mitochondrial space. The structural resemblance of PRELI-like domain of SLMO1 with that of mammalian phoshatidylinositol transfer proteins (PITPs) suggest that they share similar lipid transfer mechanisms, in which access to a buried phospholipid-binding cavity is regulated by conformationally adaptable loops. PMID:26071602

  8. Link Prediction in Complex Networks: A Mutual Information Perspective

    PubMed Central

    Tan, Fei; Xia, Yongxiang; Zhu, Boyao

    2014-01-01

    Topological properties of networks are widely applied to study the link-prediction problem recently. Common Neighbors, for example, is a natural yet efficient framework. Many variants of Common Neighbors have been thus proposed to further boost the discriminative resolution of candidate links. In this paper, we reexamine the role of network topology in predicting missing links from the perspective of information theory, and present a practical approach based on the mutual information of network structures. It not only can improve the prediction accuracy substantially, but also experiences reasonable computing complexity. PMID:25207920

  9. Spectroscopic studies of charge transfer complexes between colchicine and some π acceptors

    NASA Astrophysics Data System (ADS)

    Arslan, Mustafa; Duymus, Hulya

    2007-07-01

    Charge transfer complexes between colchicine as donor and π acceptors such as tetracyanoethylene (TCNE), 2,3-dichloro-5,6-dicyano- p-benzoquinone (DDQ), p-chloranil ( p-CHL) have been studied spectrophotometrically in dichloromethane at 21 °C. The stoichiometry of the complexes was found to be 1:1 ratio by the Job method between donor and acceptors with the maximum absorption band at a wavelength of 535, 585 and 515 nm. The equilibrium constant and thermodynamic parameters of the complexes were determined by Benesi-Hildebrand and van't Hoff equations. Colchicine in pure form and in dosage form was applied in this study. The formation constants for the complexes were shown to be dependent on the structure of the electron acceptors used.

  10. Synthesis, characterization and biological studies of a charge transfer complex: 2-aminopyridinium-4-methylbenzenesulfonate.

    PubMed

    Vadivelan, Ganesan; Saravanabhavan, Munusamy; Murugesan, Venkatesan; Sekar, Marimuthu

    2015-06-15

    A single crystal charge transfer (CT) complex, 2-aminopyridinium-4-methylbenzenesulfonate (APTS) was synthesized and recrystallized by slow solvent evaporation solution growth method at room temperature. The complex has been characterized with the elemental analysis, UV-visible, infrared (IR), (1)H and (13)C nuclear magnetic resonance (NMR) spectra. Thermogravimetric (TG) and differential thermal analysis (DTA) were reported the thermal behaviour of the complex. Single crystal XRD studies showed that the orthorhombic nature of the crystal with space group Pbca. The biological activities of CT complex, such as DNA binding and antioxidant activity has been carried out. The results indicated that the compound could interact with DNA through intercalation and show significant capacity of scavenging with 2,2-diphenyl-2-picryl-hydrazyl (DPPH). PMID:25796016

  11. Comparison of different substrates for laser-induced electron transfer desorption/ionization of metal complexes

    NASA Astrophysics Data System (ADS)

    Grechnikov, A. A.; Georgieva, V. B.; Donkov, N.; Borodkov, A. S.; Pento, A. V.; Raicheva, Z. G.; Yordanov, Tc A.

    2016-03-01

    Four different substrates, namely, graphite, tungsten, amorphous silicon (α-Si) and titanium dioxide (TiO2) films, were compared in view of the laser-induced electron transfer desorption/ionization (LETDI) of metal coordination complexes. A rhenium complex with 8-mercaptoquinoline, a copper complex with diphenylthiocarbazone and chlorophyll A were studied as the test analytes. The dependencies of the ion yield and the surface temperature on the incident radiation fluence were investigated experimentally and theoretically. The temperature was estimated using the numerical solution of a one-dimensional heat conduction problem with a heat source distributed in time and space. It was found that at the same temperature, the ion yield from the different substrates varies in the range of three orders of magnitude. The direct comparison of all studied substrates revealed that LETDI from the TiO2 and α-Si films offer a better choice for producing molecular ions of metal coordination complexes.

  12. Synthesis, characterization and biological studies of a charge transfer complex: 2-Aminopyridinium-4-methylbenzenesulfonate

    NASA Astrophysics Data System (ADS)

    Vadivelan, Ganesan; Saravanabhavan, Munusamy; Murugesan, Venkatesan; Sekar, Marimuthu

    2015-06-01

    A single crystal charge transfer (CT) complex, 2-aminopyridinium-4-methylbenzenesulfonate (APTS) was synthesized and recrystallized by slow solvent evaporation solution growth method at room temperature. The complex has been characterized with the elemental analysis, UV-visible, infrared (IR), 1H and 13C nuclear magnetic resonance (NMR) spectra. Thermogravimetric (TG) and differential thermal analysis (DTA) were reported the thermal behaviour of the complex. Single crystal XRD studies showed that the orthorhombic nature of the crystal with space group Pbca. The biological activities of CT complex, such as DNA binding and antioxidant activity has been carried out. The results indicated that the compound could interact with DNA through intercalation and show significant capacity of scavenging with 2,2-diphenyl-2-picryl-hydrazyl (DPPH).

  13. Intramolecular complex formation and triplet energy transfer in polynorbornenes incorporating benzophenone

    SciTech Connect

    Fossum, R.D.; Fox, M.A.

    1997-02-12

    The photophysical properties of homopolymers (2) and block copolymers (3) prepared by ring-opening metathesis polymerization of norbornenes substituted with benzophenone, naphthalene, and phenanthrene groups (1) have been investigated. When benzophenone is attached to this polynorbornene backbone, its excited state behavior differs from that observed for monomeric benzophenone. A new intramolecular excited state complex can be observed in the transient absorption and emission measurements of the benzophenone-substituted homopolymer. In copolymers bearing benzophenone and naphthalene or phenanthrene substituent blocks, triplet energy transfer from the sensitizer (benzophenone) to the arene is observed. This energy transfer dominates over the intramolecular complexation that characterizes group interactions in the homopolymer. 41 refs., 14 figs., 7 tabs.

  14. Formation of Stable Cationic Lipid/DNA Complexes for Gene Transfer

    NASA Astrophysics Data System (ADS)

    Hofland, Hans E. J.; Shephard, Lee; Sullivan, Sean M.

    1996-07-01

    Stable cationic lipid/DNA complexes were formed by solubilizing cationic liposomes with 1% octylglucoside and complexing a DNA plasmid with the lipid in the presence of detergent. Removal of the detergent by dialysis yielded a lipid/DNA suspension that was able to transfect tissue culture cells up to 90 days after formation with no loss in activity. Similar levels of gene transfer were obtained by mixing the cationic lipid in a liposome form with DNA just prior to cell addition. However, expression was completely lost 24 hr after mixing. The transfection efficiency of the stable complex in 15% fetal calf serum was 30% of that obtained in the absence of serum, whereas the transient complex was completely inactivated with 2% fetal calf serum. A 90-day stability study comparing various storage conditions showed that the stable complex could be stored frozen or as a suspension at 4 degrees C with no loss in transfection efficiency. Centrifugation of the stable complex produced a pellet that contained approximately 90% of the DNA and 10% of the lipid. Transfection of cells with the resuspended pellet and the supernatant showed that the majority of the transfection activity was in the pellet and all the toxicity was in the supernatant. Formation of a stable cationic lipid/DNA complex has produced a transfection vehicle that can be stored indefinitely, can be concentrated with no loss in transfection efficiency, and the toxicity levels can be greatly reduced when the active complex is isolated from the uncomplexed lipid.

  15. Study of charge transfer complexes of menadione (vitamin K3) with a series of anilines.

    PubMed

    Pal, Purnendu; Saha, Avijit; Mukherjee, Asok K; Mukherjee, Dulal C

    2004-01-01

    Menadione (vitamin K(3)) has been shown to form charge transfer complexes with N,N-dimethyl aniline, N,N-dimethyl p-toluidine and N,N-dimethyl m-toluidine in CCl(4) medium. The CT transition energies are well correlated with the ionisation potentials of the anilines. The formation constants of the complexes have been determined at a number of temperatures from which the enthalpies and entropies of formation have been obtained. The formation constants exhibit a very good linear free energy relationship (Hammett) at all the temperatures studied. PMID:14670474

  16. Theoretical evidence of photo-induced charge transfer from DNA to intercalated ruthenium (II) organometallic complexes

    NASA Astrophysics Data System (ADS)

    Chantzis, Agisilaos; Very, Thibaut; Daniel, Chantal; Monari, Antonio; Assfeld, Xavier

    2013-07-01

    The absorption spectrum of two ruthenium (II) organometallic complexes intercalated into DNA is studied at the quantum mechanic/molecular mechanic level. The macromolecular environment is taken into account as to include geometric, electrostatic and polarization effects that can alter the excitation energy and oscillator strength. The inclusion of DNA base pairs into the quantum mechanic partition allows us for the first time to clearly evidence the presence of charge transfer excited states involving an electron withdraw from DNA base pairs to the organometallic complex.

  17. Information processing in neural networks with the complex dynamic thresholds

    NASA Astrophysics Data System (ADS)

    Kirillov, S. Yu.; Nekorkin, V. I.

    2016-06-01

    A control mechanism of the information processing in neural networks is investigated, based on the complex dynamic threshold of the neural excitation. The threshold properties are controlled by the slowly varying synaptic current. The dynamic threshold shows high sensitivity to the rate of the synaptic current variation. It allows both to realize flexible selective tuning of the network elements and to provide nontrivial regimes of neural coding.

  18. Rare Earth Complex as Electron Trapper and Energy Transfer Ladder for Efficient Red Iridium Complex Based Electroluminescent Devices.

    PubMed

    Zhou, Liang; Li, Leijiao; Jiang, Yunlong; Cui, Rongzhen; Li, Yanan; Zhao, Xuesen; Zhang, Hongjie

    2015-07-29

    In this work, we experimentally demonstrated the new functions of trivalent rare earth complex in improving the electroluminescent (EL) performances of iridium complex by codoping trace Eu(TTA)3phen (TTA = thenoyltrifluoroacetone, phen = 1,10-phenanthroline) into a light-emitting layer based on PQ2Ir(dpm) (iridium(III)bis(2-phenylquinoly-N,C(2'))dipivaloylmethane). Compared with a reference device, the codoped devices displayed higher efficiencies, slower efficiency roll-off, higher brightness, and even better color purity. Experimental results demonstrated that Eu(TTA)3phen molecules function as electron trappers due to its low-lying energy levels, which are helpful in balancing holes and electrons and in broadening recombination zone. In addition, the matched triplet energy of Eu(TTA)3phen is instrumental in facilitating energy transfer from host to emitter. Finally, highly efficient red EL devices with the highest current efficiency, power efficiency and brightness up to 58.98 cd A(-1) (external quantum efficiency (EQE) of 21%), 61.73 lm W(-1) and 100870 cd m(-2), respectively, were obtained by appropriately decreasing the doping concentration of iridium complex. At certain brightness of 1000 cd m(-2), EL current efficiency up to 51.94 cd A(-1) (EQE = 18.5%) was retained. Our investigation extends the application of rare earth complexes in EL devices and provides a chance to improve the device performances. PMID:26173649

  19. Spectrophotometric study of the charge-transfer and ion-pair complexation of methamphetamine with some acceptors

    NASA Astrophysics Data System (ADS)

    Shahdousti, Parvin; Aghamohammadi, Mohammad; Alizadeh, Naader

    2008-04-01

    The charge-transfer (CT) complexes of methamphetamine (MPA) as a n-donor with several acceptors including bromocresolgreen (BCG), bromocresolpurple (BCP), chlorophenolred (CPR), picric acid (PIC), and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) have been studied spectrophotometrically in chloroform solutions in order to obtain some information about their stoichiometry and stability of complexation. The oscillator strengths, transition dipole moments and resonance energy of the complex in the ground state for all complexes have been calculated. Vertical ionization potential of MPA and electron affinity of acceptors were determined by ab initio calculation. The acceptors were also used to utilize a simple and sensitive extraction-spectrophotometric method for the determination of MPA. The method is based on the formation of 1:1 ion-pair association complexes of MPA with BCG, BCP and PIC in chloroform medium. Beer's plots were obeyed in a general concentration range of 0.24-22 μg ml -1 for the investigated drug with different acceptors. The proposed methods were applied successfully for the determination of MAP in pure and abuse drug with good accuracy and precision.

  20. Charge-transfer complexes of sulfamethoxazole drug with different classes of acceptors

    NASA Astrophysics Data System (ADS)

    Refat, Moamen S.; El-Korashy, Sabry A.; El-Deen, Ibrahim M.; El-Sayed, Shaima M.

    2010-09-01

    The charge-transfer complexes of the donor sulfamethoxazole (SZ) with iodine (I 2), 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), p-chloranil (CHL) and picric acid (PA) have been studied spectrophotometrically in chloroform or methanol at room temperature using absorption spectrophotometer. The results indicate that formation of CT-complexes in case of four acceptors. The stoichiometry of the complexes was found to be 1:1 ratio by molar ratio method between donor and acceptor with maximum absorption bands (CT band). The data are discussed in terms of formation constant ( KCT), molar extinction coefficient ( ɛCT), standard free energy (Δ G°), oscillator strength (ƒ), transition dipole moment ( μ), resonance energy ( RN) and ionization potential ( ID). The results indicate that the formation constant ( KCT) for the complexes were shown to be dependent upon the nature of electron acceptor, donor and polarity of solvents which were used. IR, 1H NMR, mass spectra, UV-Vis techniques, elemental analyses (CHN) and TG-DTG investigation were used to characterize the four sulfamethoxazole charge-transfer complexes.

  1. Catalytic Transfer Hydrogenation with a Methandiide-Based Carbene Complex: An Experimental and Computational Study.

    PubMed

    Weismann, Julia; Gessner, Viktoria H

    2015-11-01

    The transfer hydrogenation (TH) reaction of ketones with catalytic systems based on a methandiide-derived ruthenium carbene complex was investigated and optimised. The complex itself makes use of the noninnocent behaviour of the carbene ligand (M=CR2 →MH-C(H)R2 ), but showed only moderate activity, thus requiring long reaction times to achieve sufficient conversion. DFT studies on the reaction mechanism revealed high reaction barriers for both the dehydrogenation of iPrOH and the hydrogen transfer. A considerable improvement of the catalytic activity could be achieved by employing triphenylphosphine as additive. Mechanistic studies on the role of PPh3 in the catalytic cycle revealed the formation of a cyclometalated complex upon phosphine coordination. This ruthenacycle was revealed to be the active species under the reaction conditions. The use of the isolated complex resulted in high catalytic activities in the TH of aromatic as well as aliphatic ketones. The complex was also found to be active under base-free conditions, suggesting that the cyclometalation is crucial for the enhanced activity. PMID:26403918

  2. Photophysical studies of metal to ligand charge transfer involving quadruply bonded complexes of molybdenum and tungsten.

    PubMed

    Chisholm, Malcolm H; Brown-Xu, Samantha E; Spilker, Thomas F

    2015-03-17

    Photoinduced metal-to-ligand charge transfer transitions afford numerous applications in terms of photon energy harvesting. The majority of metal complexes studied to date involve diamagnetic systems of d(6), d(8), and d(10) transition metals. These typically have very short-lived, ∼100 fs, singlet metal to ligand charge transfer ((1)MLCT) states that undergo intersystem crossing to triplet metal to ligand charge transfer ((3)MLCT) states that are longer lived and are responsible for much of the photophysical studies. In contrast, the metal-metal quadruply bonded complexes of molybdenum and tungsten supported by carboxylate, O2CR, and related amidinate ligands (RN)2C(R') have relatively long-lived (1)MLCT states arising from M2δ to Lπ* transitions. These have lifetimes in the range 1-20 ps prior to intersystem crossing to T1 states that may be (3)MLCT or (3)MMδδ* with lifetimes of 1-100 ns and 1-100 μs, respectively. The M2 quadruply bonded complexes take the form M2L4 or M2L4-nL'n where n = 1-3. Thus, in their photoexcited MLCT states, these compounds pose the question of how the charge resides on the ligands. This Account reviews the current knowledge of how charge is positioned with time in S1 and T1 states with the aid of active IR reported groups located on the ligands, for example, C≡X multiple bonds (X = C, N, or O). Several examples of localized and delocalized charge distributions are noted along with kinetic barriers to the interconversion of MLCT and δδ* states. On the 50th anniversary of the recognition of the MM quadruple bond, these complexes are revealing some remarkable features in the study of the photophysical properties of metal-ligand charge transfer states. PMID:25695495

  3. Electrocatalytic Hydrogen Production by an Aluminum(III) Complex: Ligand-Based Proton and Electron Transfer.

    PubMed

    Thompson, Emily J; Berben, Louise A

    2015-09-28

    Environmentally sustainable hydrogen-evolving electrocatalysts are key in a renewable fuel economy, and ligand-based proton and electron transfer could circumvent the need for precious metal ions in electrocatalytic H2 production. Herein, we show that electrocatalytic generation of H2 by a redox-active ligand complex of Al(3+) occurs at -1.16 V vs. SCE (500 mV overpotential). PMID:26249108

  4. Reconstruction of complex signals using minimum Rényi information.

    PubMed

    Frieden, B R; Bajkova, A T

    1995-07-10

    An information divergence, such as Shannon mutual information, measures the distance between two probability-density functions (or images). A wide class of such measures, called α divergences, with desirable properties such as convexity over all space, was defined by Amari. Rényi's information Dα is an α divergence. Because of its convexity property, the minimum of Dα is easily attained. Minimization accomplishes minimum distance (maximum resemblance) between an unknown image and a known reference image. Such a biasing effect permits complex images, such as occur in inverse syntheticaperture- radar imaging, to be well reconstructed. The algorithm permits complex amplitudes to replace the probabilities in the Rényi form. The bias image may be constructed as a smooth version of the linear, Fourier reconstruction of the data. Examples on simulated complex image data with and without noise indicate that the Rényi reconstruction approach permits superresolution in low-noise cases and higher fidelity than ordinary, linear reconstructions in higher-noise cases. PMID:21052233

  5. Electron transfer between the QmoABC membrane complex and adenosine 5'-phosphosulfate reductase.

    PubMed

    Duarte, Américo G; Santos, André A; Pereira, Inês A C

    2016-04-01

    The dissimilatory adenosine 5'-phosphosulfate reductase (AprAB) is a key enzyme in the sulfate reduction pathway that catalyzes the reversible two electron reduction of adenosine 5'-phosphosulfate (APS) to sulfite and adenosine monophosphate (AMP). The physiological electron donor for AprAB is proposed to be the QmoABC membrane complex, coupling the quinone-pool to sulfate reduction. However, direct electron transfer between these two proteins has never been observed. In this work we demonstrate for the first time direct electron transfer between the Desulfovibrio desulfuricans ATCC 27774 QmoABC complex and AprAB. Cyclic voltammetry conducted with the modified Qmo electrode and AprAB in the electrolyte solution presented the Qmo electrochemical signature with two additional well-defined one electron redox processes, attributed to the AprAB FAD redox behavior. Moreover, experiments performed under catalytic conditions using the QmoABC modified electrode, with AprAB and APS in solution, show a catalytic current peak develop in the cathodic wave, attributed to substrate reduction, and which is not observed in the absence of QmoABC. Substrate dependence conducted with different electrode preparations (with and without immobilized Qmo) demonstrated that the QmoABC complex is essential for efficient electron delivery to AprAB, in order to sustain catalysis. These results confirm the role of Qmo in electron transfer to AprAB. PMID:26768116

  6. 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

  7. Structure and electronic spectra of purine-methyl viologen charge transfer complexes.

    PubMed

    Jalilov, Almaz S; Patwardhan, Sameer; Singh, Arunoday; Simeon, Tomekia; Sarjeant, Amy A; Schatz, George C; Lewis, Frederick D

    2014-01-01

    The structure and properties of the electron donor-acceptor complexes formed between methyl viologen and purine nucleosides and nucleotides in water and the solid state have been investigated using a combination of experimental and theoretical methods. Solution studies were performed using UV-vis and (1)H NMR spectroscopy. Theoretical calculations were performed within the framework of density functional theory (DFT). Energy decomposition analysis indicates that dispersion and induction (charge-transfer) interactions dominate the total binding energy, whereas electrostatic interactions are largely repulsive. The appearance of charge transfer bands in the absorption spectra of the complexes are well-described by time-dependent DFT and are further explained in terms of the redox properties of purine monomers and solvation effects. Crystal structures are reported for complexes of methyl viologen with the purines 2'-deoxyguanosine 3'-monophosphate (DAD'DAD' type) and 7-deazaguanosine (DAD'ADAD' type). Comparison of the structures determined in the solid state and by theoretical methods in solution provides valuable insights into the nature of charge-transfer interactions involving purine bases as electron donors. PMID:24294996

  8. 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

  9. Energy transfer in spectrally inhomogeneous light-harvesting pigment-protein complexes of purple bacteria.

    PubMed Central

    Hess, S; Akesson, E; Cogdell, R J; Pullerits, T; Sundström, V

    1995-01-01

    Energy transfer within the peripheral light-harvesting antenna of the purple bacteria Rhodobacter sphaeroides and Rhodopseudomonas palustris was studied by one- and two-color pump-probe absorption spectroscopy with approximately 100-fs tunable pulses at room temperature and at 77 K. The energy transfer from B800 to B850 occurs with a time constant of 0.7 +/- 0.05 ps at room temperature and 1.8 +/- 0.2 ps at 77 K and is similar in both species. Anisotropy measurements suggest a limited but fast B800 <--> B800 transfer time (tau approximately 0.3 ps). This is analyzed as incoherent hopping of the excitation in a system of spectrally inhomogeneous antenna pigment-protein complexes, by a master equation approach. The simulations show that the measured B800 dynamics is well described as energy transfer with a characteristic average nearest-neighbor pairwise transfer time of 0.35 ps among approximately 10 Bchl molecules in a circular arrangement, in good agreement with the recent high-resolution structure of LH2. The possible presence of fast intramolecular relaxation processes within the Bchl a molecule was investigated by measurement of time-resolved difference absorption spectra and kinetics of Bchl a in solution and in low-temperature glasses. From these measurements it is concluded that fast transients observed at room temperature are due mainly to solvation processes, whereas at 77 K predominantly slower (> 10-ps) relaxation occurs. Images FIGURE 11 PMID:8599629

  10. Informal Care and Inter-vivos Transfers: Results from the National Longitudinal Survey of Mature Women.

    PubMed

    Norton, Edward C; Nicholas, Lauren H; Huang, Sean Sheng-Hsiu

    2013-05-01

    Informal care is the largest source of long-term care for elderly, surpassing home health care and nursing home care. By definition, informal care is unpaid. It remains a puzzle why so many adult children give freely of their time. Transfers of time to the older generation may be balanced by financial transfers going to the younger generation. This leads to the question of whether informal care and inter-vivos transfers are causally related. We analyze data from the 1999 and 2003 waves of National Longitudinal Survey of Mature Women. We examine whether the elderly parents give more inter-vivos monetary transfers to adult children who provide informal care, by examining both the extensive and intensive margins of financial transfers and of informal care. We find statistically significant results that a child who provides informal care is more likely to receive inter-vivos transfers than a sibling who does not. If a child does provide care, there is no statistically significant effect on the amount of the transfer. PMID:25285181

  11. Information Driven Self-Organization of Complex Robotic Behaviors

    PubMed Central

    Martius, Georg; Der, Ralf; Ay, Nihat

    2013-01-01

    Information theory is a powerful tool to express principles to drive autonomous systems because it is domain invariant and allows for an intuitive interpretation. This paper studies the use of the predictive information (PI), also called excess entropy or effective measure complexity, of the sensorimotor process as a driving force to generate behavior. We study nonlinear and nonstationary systems and introduce the time-local predicting information (TiPI) which allows us to derive exact results together with explicit update rules for the parameters of the controller in the dynamical systems framework. In this way the information principle, formulated at the level of behavior, is translated to the dynamics of the synapses. We underpin our results with a number of case studies with high-dimensional robotic systems. We show the spontaneous cooperativity in a complex physical system with decentralized control. Moreover, a jointly controlled humanoid robot develops a high behavioral variety depending on its physics and the environment it is dynamically embedded into. The behavior can be decomposed into a succession of low-dimensional modes that increasingly explore the behavior space. This is a promising way to avoid the curse of dimensionality which hinders learning systems to scale well. PMID:23723979

  12. Information driven self-organization of complex robotic behaviors.

    PubMed

    Martius, Georg; Der, Ralf; Ay, Nihat

    2013-01-01

    Information theory is a powerful tool to express principles to drive autonomous systems because it is domain invariant and allows for an intuitive interpretation. This paper studies the use of the predictive information (PI), also called excess entropy or effective measure complexity, of the sensorimotor process as a driving force to generate behavior. We study nonlinear and nonstationary systems and introduce the time-local predicting information (TiPI) which allows us to derive exact results together with explicit update rules for the parameters of the controller in the dynamical systems framework. In this way the information principle, formulated at the level of behavior, is translated to the dynamics of the synapses. We underpin our results with a number of case studies with high-dimensional robotic systems. We show the spontaneous cooperativity in a complex physical system with decentralized control. Moreover, a jointly controlled humanoid robot develops a high behavioral variety depending on its physics and the environment it is dynamically embedded into. The behavior can be decomposed into a succession of low-dimensional modes that increasingly explore the behavior space. This is a promising way to avoid the curse of dimensionality which hinders learning systems to scale well. PMID:23723979

  13. Workshop on Possibilities for Improving Information Transfer. Discussion Guide.

    ERIC Educational Resources Information Center

    United Nations Educational, Scientific, and Cultural Organization, Paris (France).

    The following topics are discussed to show various forms for cooperative ventures in the information field which countries within a region might consider: (1) building up basic resources, collections, and stores; (2) collective retrieval tools to the combined resources of the region; (3) regional information service activities; (4) communication…

  14. NMR-derived Topology of a GFP-photoprotein Energy Transfer Complex*

    PubMed Central

    Titushin, Maxim S.; Feng, Yingang; Stepanyuk, Galina A.; Li, Yang; Markova, Svetlana V.; Golz, Stefan; Wang, Bi-Cheng; Lee, John; Wang, Jinfeng; Vysotski, Eugene S.; Liu, Zhi-Jie

    2010-01-01

    Förster resonance energy transfer within a protein-protein complex has previously been invoked to explain emission spectral modulation observed in several bioluminescence systems. Here we present a spatial structure of a complex of the Ca2+-regulated photoprotein clytin with its green-fluorescent protein (cgGFP) from the jellyfish Clytia gregaria, and show that it accounts for the bioluminescence properties of this system in vitro. We adopted an indirect approach of combining x-ray crystallography determined structures of the separate proteins, NMR spectroscopy, computational docking, and mutagenesis. Heteronuclear NMR spectroscopy using variously 15N,13C,2H-enriched proteins enabled assignment of backbone resonances of more than 94% of the residues of both proteins. In a mixture of the two proteins at millimolar concentrations, complexation was inferred from perturbations of certain 1H-15N HSQC-resonances, which could be mapped to those residues involved at the interaction site. A docking computation using HADDOCK was employed constrained by the sites of interaction, to deduce an overall spatial structure of the complex. Contacts within the clytin-cgGFP complex and electrostatic complementarity of interaction surfaces argued for a weak protein-protein complex. A weak affinity was also observed by isothermal titration calorimetry (KD = 0.9 mm). Mutation of clytin residues located at the interaction site reduced the degree of protein-protein association concomitant with a loss of effectiveness of cgGFP in color-shifting the bioluminescence. It is suggested that this clytin-cgGFP structure corresponds to the transient complex previously postulated to account for the energy transfer effect of GFP in the bioluminescence of aequorin or Renilla luciferase. PMID:20926380

  15. Integrated computational and conceptual solutions for complex environmental information management

    NASA Astrophysics Data System (ADS)

    Rückemann, Claus-Peter

    2016-06-01

    This paper presents the recent results of the integration of computational and conceptual solutions for the complex case of environmental information management. The solution for the major goal of creating and developing long-term multi-disciplinary knowledge resources and conceptual and computational support was achieved by implementing and integrating key components. The key components are long-term knowledge resources providing required structures for universal knowledge creation, documentation, and preservation, universal multi-disciplinary and multi-lingual conceptual knowledge and classification, especially, references to Universal Decimal Classification (UDC), sustainable workflows for environmental information management, and computational support for dynamical use, processing, and advanced scientific computing with Integrated Information and Computing System (IICS) components and High End Computing (HEC) resources.

  16. Encoding techniques for complex information structures in connectionist systems

    NASA Technical Reports Server (NTRS)

    Barnden, John; Srinivas, Kankanahalli

    1990-01-01

    Two general information encoding techniques called relative position encoding and pattern similarity association are presented. They are claimed to be a convenient basis for the connectionist implementation of complex, short term information processing of the sort needed in common sense reasoning, semantic/pragmatic interpretation of natural language utterances, and other types of high level cognitive processing. The relationships of the techniques to other connectionist information-structuring methods, and also to methods used in computers, are discussed in detail. The rich inter-relationships of these other connectionist and computer methods are also clarified. The particular, simple forms are discussed that the relative position encoding and pattern similarity association techniques take in the author's own connectionist system, called Conposit, in order to clarify some issues and to provide evidence that the techniques are indeed useful in practice.

  17. Geometry and quadratic nonlinearity of charge transfer complexes in solution: A theoretical study

    SciTech Connect

    Mukhopadhyay, S.; Ramasesha, S.; Pandey, Ravindra; Das, Puspendu K.

    2011-01-28

    In this paper, we have computed the quadratic nonlinear optical (NLO) properties of a class of weak charge transfer (CT) complexes. These weak complexes are formed when the methyl substituted benzenes (donors) are added to strong acceptors like chloranil (CHL) or di-chloro-di-cyano benzoquinone (DDQ) in chloroform or in dichloromethane. The formation of such complexes is manifested by the presence of a broad absorption maximum in the visible range of the spectrum where neither the donor nor the acceptor absorbs. The appearance of this visible band is due to CT interactions, which result in strong NLO responses. We have employed the semiempirical intermediate neglect of differential overlap (INDO/S) Hamiltonian to calculate the energy levels of these CT complexes using single and double configuration interaction (SDCI). The solvent effects are taken into account by using the self-consistent reaction field (SCRF) scheme. The geometry of the complex is obtained by exploring different relative molecular geometries by rotating the acceptor with respect to the fixed donor about three different axes. The theoretical geometry that best fits the experimental energy gaps, {beta}{sub HRS} and macroscopic depolarization ratios is taken to be the most probable geometry of the complex. Our studies show that the most probable geometry of these complexes in solution is the parallel displaced structure with a significant twist in some cases.

  18. Assessing the Suitability of Process and Information Technology in Supporting Tacit Knowledge Transfer

    ERIC Educational Resources Information Center

    Wu, Chien-Hsing; Kao, Shu-Chen; Shih, Lan-Hsin

    2010-01-01

    The transfer of tacit knowledge, one of the most important issues in the knowledge sharing context, needs a multi-dimensional perception in its process. Information technology's (IT) supporting role has already been addressed in the process of tacit knowledge transfer. However, IT has its own characteristics, and in turn, may have dissimilar…

  19. The Effectiveness and Feasibility of a TRISNET Regional Center in Information Transfer. Final Report.

    ERIC Educational Resources Information Center

    Rath, Gustave J.; And Others

    A study was conducted to assess the feasibility of establishing a regional information transfer center within the context of the National Network of Transportation Research Information Services (TRISNET). The principle areas of investigation were: (1) the transportation information needs of the public and private sectors; (2) the utility of…

  20. Analysis of Technological Information Transfer among Japanese Computer Scientists at a Research Front.

    ERIC Educational Resources Information Center

    Takayama, Masaya

    1986-01-01

    Describes the methodology and results of a study that examined information flow at the technological research front by analyzing a Japanese national project in computer technology. Various formats of information dissemination are identified, and a classification of researchers and engineers by information transfer activities is presented. (4…

  1. 77 FR 4815 - Ace Info Solutions, Inc., and Information International Associates; Transfer of Data

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-01-31

    ...This notice announces that pesticide related information submitted to EPA's Office of Pesticide Programs (OPP) pursuant to the Federal Insecticide, Fungicide, and Rodenticide Act (FIFRA) and the Federal Food, Drug, and Cosmetic Act (FFDCA), including information that may have been claimed as Confidential Business Information (CBI) by the submitter, will be transferred to Ace Info Solutions,......

  2. HIV-1 Integrase Strand Transfer Inhibitors Stabilize an Integrase-Single Blunt-Ended DNA Complex

    PubMed Central

    Bera, Sibes; Pandey, Krishan K.; Vora, Ajaykumar C.; Grandgenett, Duane P.

    2011-01-01

    Summary Integration of HIV (human immunodeficiency virus) cDNA ends by integrase (IN) into host chromosomes involves a concerted integration mechanism. IN juxtaposes two DNA blunt-ends to form the synaptic complex (SC) which is the intermediate in the concerted integration pathway. SC is inactivated by strand transfer inhibitors (STI) with IC50 values of ~20 nM for inhibition of concerted integration. We detected a new nucleoprotein complex on native agarose that was produced in the presence of STI >200 nM, termed IN-single DNA (ISD) complex. Two IN dimers appear to bind in a parallel fashion at the DNA terminus producing a ~32 bp DNaseI protective footprint. In the presence of Raltegravir, MK-2048 and L-841,411, IN incorporated ~20 to 25% of the input blunt-ended DNA substrate into the stabilized ISD complex. Seven other STI also produced the ISD complex (≤ 5% of input DNA). The formation of the ISD complex was not dependent upon 3’ OH processing and the DNA was predominately blunt-ended in the complex. Raltegravir-resistant IN mutant N155H weakly form the ISD complex in the presence of Raltegravir at ~25% level of wild type IN. In contrast, MK-2048 and L-841,411 produced ~3 to 5-fold more ISD than Raltegravir with N155H IN, which is susceptible to these two inhibitors. The results suggest STI are slow binding inhibitors and the potency to form and stabilize the ISD complex is not always related to inhibition of concerted integration. Rather, the apparent binding and dissociation properties of each STI influenced the production of the ISD complex. PMID:21295584

  3. Computational Confirmation of the Carrier for the "XCN" Interstellar Ice Bank: OCN(-) Charge Transfer Complexes

    NASA Technical Reports Server (NTRS)

    Park, J.-Y.; Woon, D. E.

    2004-01-01

    Recent experimental studies provide evidence that carrier for the so-called XCN feature at 2165 cm(exp -1) (4.62 micron) in young stellar objects is an OCN(-)/NH4(+) charge transfer (CT) complex that forms in energetically processed interstellar icy grain mantles. Although other RCN nitriles and RCN iosonitriles have been considered, Greenberg's conjecture that OCN(-) is associated with the XCN feature has persisted for over 15 years. In this work we report a computational investigation that thoroughly confirms the hypothesis that the XCN feature observed in laboratory studies can result from OCN(-)/NH4(+) CT complexes arising from HNCO and NH3, in a water ice environment. Density functional theory calculations with theory calculations with HNCO, NH3, and up to 12 waters reproduce seven spectroscopic measurements associated with XCN: the band origin of the asymmetric stretching mode of OCN(-), shifts due to isotopic substitutions of C, N, O, and H, and two weak features. However, very similar values are also found for the OCN(-)/NH4(+) CT complex arising from HOCN and NH3. In both cases, the complex forms by barrierless proton transfer from HNCO or HOCN to NH3 during the optimization of the solvated system. Scaled B3LYP/6-31+G** harmonic frequencies for HNCO and HOCN cases are 2181 and 2202 cm(exp -1), respectively.

  4. Laser desorption/ionization mass spectrometry of diesel particulate matter with charge-transfer complexes.

    PubMed

    Carré, Vincent; Vernex-Loset, Lionel; Krier, Gabriel; Manuelli, Pascal; Muller, Jean-François

    2004-07-15

    Polycyclic aromatic hydrocarbons (PAHs) are often associated with complex matrixes such as exhaust diesel particulate matter (DPM), which complicates their study. In that case, laser desorption/ionization mass spectrometry is one of the techniques which ensures their direct analysis in the solid state. We demonstrate in this paper that the use of charge-transfer pi-complexing agents allows us to selectively detect by Fourier transform ion cyclotron resonance mass spectrometry PAHs adsorbed on diesel particles with high sensitivity. 2,4,7-trinitro-9-fluorenone and 7,7',8,8'-tetracyanoquinodimethane pi-acceptor compounds form charge-transfer complexes with PAHs and prevent their evaporation in the mass spectrometer during analysis. Moreover, the production of PAH molecular ions is dramatically increased by laser irradiation of these complexes at short wavelength (221.7 nm) and low power density (5 x 10(6) W cm(-)(2)). This methodology is applied for the first time to the examination of DPM collected during the new European driving cycle for light-duty vehicles. Differentiation criteria may coherently be assigned to engine operating mode (engine temperature, driving conditions). DPM samples can also be easily distinguished in negative ions according to the high sensitivity of this detection mode to sulfate compounds. PMID:15253632

  5. Charge-transfer optical absorption mechanism of DNA:Ag-nanocluster complexes

    NASA Astrophysics Data System (ADS)

    Longuinhos, R.; Lúcio, A. D.; Chacham, H.; Alexandre, S. S.

    2016-05-01

    Optical properties of DNA:Ag-nanoclusters complexes have been successfully applied experimentally in Chemistry, Physics, and Biology. Nevertheless, the mechanisms behind their optical activity remain unresolved. In this work, we present a time-dependent density functional study of optical absorption in DNA:Ag4. In all 23 different complexes investigated, we obtain new absorption peaks in the visible region that are not found in either the isolated Ag4 or isolated DNA base pairs. Absorption from red to green are predominantly of charge-transfer character, from the Ag4 to the DNA fragment, while absorption in the blue-violet range are mostly associated to electronic transitions of a mixed character, involving either DNA-Ag4 hybrid orbitals or intracluster orbitals. We also investigate the role of exchange-correlation functionals in the calculated optical spectra. Significant differences are observed between the calculations using the PBE functional (without exact exchange) and the CAM-B3LYP functional (which partly includes exact exchange). Specifically, we observe a tendency of charge-transfer excitations to involve purines bases, and the PBE spectra error is more pronounced in the complexes where the Ag cluster is bound to the purines. Finally, our results also highlight the importance of adding both the complementary base pair and the sugar-phosphate backbone in order to properly characterize the absorption spectrum of DNA:Ag complexes.

  6. Electrostatics, hydration, and proton transfer dynamics in the membrane domain of respiratory complex I

    PubMed Central

    Kaila, Ville R. I.; Wikström, Mårten; Hummer, Gerhard

    2014-01-01

    Complex I serves as the primary electron entry point into the mitochondrial and bacterial respiratory chains. It catalyzes the reduction of quinones by electron transfer from NADH, and couples this exergonic reaction to the translocation of protons against an electrochemical proton gradient. The membrane domain of the enzyme extends ∼180 Å from the site of quinone reduction to the most distant proton pathway. To elucidate possible mechanisms of the long-range proton-coupled electron transfer process, we perform large-scale atomistic molecular dynamics simulations of the membrane domain of complex I from Escherichia coli. We observe spontaneous hydration of a putative proton entry channel at the NuoN/K interface, which is sensitive to the protonation state of buried glutamic acid residues. In hybrid quantum mechanics/classical mechanics simulations, we find that the observed water wires support rapid proton transfer from the protein surface to the center of the membrane domain. To explore the functional relevance of the pseudosymmetric inverted-repeat structures of the antiporter-like subunits NuoL/M/N, we constructed a symmetry-related structure of a possible alternate-access state. In molecular dynamics simulations, we find the resulting structural changes to be metastable and reversible at the protein backbone level. However, the increased hydration induced by the conformational change persists, with water molecules establishing enhanced lateral connectivity and pathways for proton transfer between conserved ionizable residues along the center of the membrane domain. Overall, the observed water-gated transitions establish conduits for the unidirectional proton translocation processes, and provide a possible coupling mechanism for the energy transduction in complex I. PMID:24778264

  7. Information transfer in pilots' use of a collision avoidance system

    NASA Technical Reports Server (NTRS)

    Chappell, Sheryl L.; Scott, Barry C.; Billings, Charles E.

    1987-01-01

    A flight simulator study of pilots' use of the Traffic-alert and Collision Avoidance System is described. Three levels of information on the location of other air traffic were presented to different groups of airline pilots. The amount of informtion on the location of other traffic had little effect on pilots' performance of the maneuvers commanded by the collision avoidance system. Measured crew responses were similar with no presentation of traffic location, with limited information, and with continuous traffic information. No learning effects were observed, and differences in flight experience did not contribute to the performance difference found.

  8. 77 FR 34127 - Financial Management Service; Proposed Collection of Information: Electronic Transfer Account...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-06-08

    ... Fiscal Service Financial Management Service; Proposed Collection of Information: Electronic Transfer Account (ETA) Financial Agency Agreement AGENCY: Financial Management Service, Fiscal Service, Treasury. ACTION: Notice and Request for comments. SUMMARY: The Financial Management Service, as part of...

  9. SNP Markers as Additional Information to Resolve Complex Kinship Cases

    PubMed Central

    Pontes, M. Lurdes; Fondevila, Manuel; Laréu, Maria Victoria; Medeiros, Rui

    2015-01-01

    Summary Background DNA profiling with sets of highly polymorphic autosomal short tandem repeat (STR) markers has been applied in various aspects of human identification in forensic casework for nearly 20 years. However, in some cases of complex kinship investigation, the information provided by the conventionally used STR markers is not enough, often resulting in low likelihood ratio (LR) calculations. In these cases, it becomes necessary to increment the number of loci under analysis to reach adequate LRs. Recently, it has been proposed that single nucleotide polymorphisms (SNPs) could be used as a supportive tool to STR typing, eventually even replacing the methods/markers now employed. Methods In this work, we describe the results obtained in 7 revised complex paternity cases when applying a battery of STRs, as well as 52 human identification SNPs (SNPforID 52plex identification panel) using a SNaPshot methodology followed by capillary electrophoresis. Results Our results show that the analysis of SNPs, as complement to STR typing in forensic casework applications, would at least increase by a factor of 4 total PI values and correspondent Essen-Möller's W value. Conclusions We demonstrated that SNP genotyping could be a key complement to STR information in challenging casework of disputed paternity, such as close relative individualization or complex pedigrees subject to endogamous relations. PMID:26733770

  10. Computer Center: BASIC String Models of Genetic Information Transfer.

    ERIC Educational Resources Information Center

    Spain, James D., Ed.

    1984-01-01

    Discusses some of the major genetic information processes which may be modeled by computer program string manipulation, focusing on replication and transcription. Also discusses instructional applications of using string models. (JN)

  11. Identifying the magnetoconductance responses by the induced charge transfer complex states in pentacene-based diodes

    NASA Astrophysics Data System (ADS)

    Huang, Wei-Shun; Lee, Tsung-Hsun; Guo, Tzung-Fang; Huang, J. C. A.; Wen, Ten-Chin

    2012-07-01

    We investigate the magnetoconductance (MC) responses in photocurrent, unipolar injection, and bipolar injection regimes in pentacene-based diodes. Both photocurrent and bipolar injection contributed MC responses show large difference in MC line shape, which are attributed to triplet-polaron interaction modulated by the magnetic field dependent singlet fission and the intersystem crossing of the polaron pair, respectively. By blending 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane into pentacene, all the MC responses are suppressed but the MC response at unipolar injection regime is enhanced, which is attributed to the induced charge transfer complex states (CT complex states). This work identify the MC responses between single carrier contributed MC and exciton related MC by the induced CT complex states.

  12. Energy-Efficient Information Transfer by Visual Pathway Synapses

    PubMed Central

    Harris, Julia J.; Jolivet, Renaud; Engl, Elisabeth; Attwell, David

    2015-01-01

    Summary The architecture of computational devices is shaped by their energy consumption. Energetic constraints are used to design silicon-based computers but are poorly understood for neural computation. In the brain, most energy is used to reverse ion influxes generating excitatory postsynaptic currents (EPSCs) and action potentials. Thus, EPSCs should be small to minimize energy use, but not so small as to impair information transmission. We quantified information flow through the retinothalamic synapse in the visual pathway in brain slices, with cortical and inhibitory input to the postsynaptic cell blocked. Altering EPSC size with dynamic clamp, we found that a larger-than-normal EPSC increased information flow through the synapse. Thus, the evolutionarily selected EPSC size does not maximize retinal information flow to the cortex. By assessing the energy used on postsynaptic ion pumping and action potentials, we show that, instead, the EPSC size optimizes the ratio of retinal information transmitted to energy consumed. These data suggest maximization of information transmission per energy used as a synaptic design principle. PMID:26671670

  13. Information systems and technology transfer programs on geothermal energy and other renewable sources of energy

    SciTech Connect

    Lippmann, Marcelo J.; Antunez, Emilio u.

    1996-01-24

    In order to remain competitive it is necessary to stay informed and use the most advanced technologies available. Recent developments in communication, like the Internet and the World Wide Web, enormously facilitate worldwide data and technology transfer. A compilation of the most important sources of data on renewable energies, especially geothermal, as well as lists of relevant technology transfer programs are presented. Information on how to gain access to, and learn more about them is also given.

  14. Reinforcing Visual Grouping Cues to Communicate Complex Informational Structure.

    PubMed

    Bae, Juhee; Watson, Benjamin

    2014-12-01

    In his book Multimedia Learning [7], Richard Mayer asserts that viewers learn best from imagery that provides them with cues to help them organize new information into the correct knowledge structures. Designers have long been exploiting the Gestalt laws of visual grouping to deliver viewers those cues using visual hierarchy, often communicating structures much more complex than the simple organizations studied in psychological research. Unfortunately, designers are largely practical in their work, and have not paused to build a complex theory of structural communication. If we are to build a tool to help novices create effective and well structured visuals, we need a better understanding of how to create them. Our work takes a first step toward addressing this lack, studying how five of the many grouping cues (proximity, color similarity, common region, connectivity, and alignment) can be effectively combined to communicate structured text and imagery from real world examples. To measure the effectiveness of this structural communication, we applied a digital version of card sorting, a method widely used in anthropology and cognitive science to extract cognitive structures. We then used tree edit distance to measure the difference between perceived and communicated structures. Our most significant findings are: 1) with careful design, complex structure can be communicated clearly; 2) communicating complex structure is best done with multiple reinforcing grouping cues; 3) common region (use of containers such as boxes) is particularly effective at communicating structure; and 4) alignment is a weak structural communicator. PMID:26356911

  15. STRUCTURAL ANALYSIS OF ALTERNATIVE COMPLEX III IN THE PHOTOSYNTHETIC ELECTRON TRANSFER CHAIN OF CHLOROFLEXUS AURANTIACUS

    PubMed Central

    Gao, Xinliu; Xin, Yueyong; Bell, Patrick D.; Wen, Jianzhong; Blankenship, Robert E.

    2010-01-01

    The green photosynthetic bacterium Chloroflexus aurantiacus, which belongs to the phylum of filamentous anoxygenic phototrophs, does not contain a cytochrome bc or bf type complex as is found in all other known groups of phototrophs. This suggests that a functional replacement exists to link the reaction center photochemistry to cyclic electron transfer as well as respiration. Earlier work identified a potential substitute of the cytochrome bc complex, now named alternative complex III (ACIII), which has been purified, identified and characterized from C. aurantiacus. ACIII functions as a menaquinol:auracyanin oxidoreductase in the photosynthetic electron transfer chain, and a related but distinct complex functions in respiratory electron flow to a terminal oxidase. In this work, we focus on elucidating the structure of the photosynthetic ACIII. We found that AC III is an integral-membrane protein complex of around 300 kDa that consists of 8 subunits of 7 different types. Among them, there are 4 metalloprotein subunits, including a 113 kDa iron-sulfur cluster-containing polypeptide, a 25 kDa penta-heme c-containing subunit and two 20 kDa mono-heme c-containing subunits in the form of a homodimer. A variety of analytical techniques were employed in determining the ACIII substructure, including HPLC combined with ESI-MS, metal analysis, potentiometric titration and intensity analysis of heme-staining SDS-PAGE. A preliminary structural model of the ACIII complex is proposed based on the analytical data and chemical cross-linking in tandem with mass analysis using MALDI-TOF, as well as transmembrane and transit peptide analysis. PMID:20614874

  16. High-Resolution Solid-State NMR Investigation of the Phase Transition in Decamethylferrocene-Acenaphthenequinone Charge-Transfer Complex

    NASA Astrophysics Data System (ADS)

    Nakamura, Hideaki; Kuwahara, Daisuke; Mochida, Tomoyuki

    2009-10-01

    A charge-transfer complex composed of decamethylferrocene (D) and acenaphthenequinone (A) was prepared. The material was a 1:1 neutral complex with a mixed-stack structure and exhibited a phase transition at -16 °C. High-resolution 13C and 1H NMR spectroscopy revealed that an inclination of A with respect to D occurs below the phase-transition temperature. The 1H spin-diffusion rates of the complex undergoing high-speed magic-angle spinning (MAS) were measured to determine the shortest 1H-1H distance r between D and A. To analyze the experimental results, we derived the analytical expression of the spin-diffusion rate Wz for a homonuclear multispin system undergoing MAS. It was found that Wz for the complex is proportional only to 1/r6 under high-speed MAS conditions. On the basis of this relationship and the crystal structure at 20 °C, it was determined that the shortest 1H-1H distance r at -27.7 °C (below the phase transition temperature) is 0.4 Å shorter than that at 20 °C. Given this information, a plausible model of the low-temperature structure is discussed.

  17. Metal transfer within the E. coli HypB-HypA complex of hydrogenase accessory proteins†

    PubMed Central

    Douglas, Colin D.; Ngu, Thanh T.; Kaluarachchi, Harini; Zamble, Deborah B.

    2015-01-01

    The maturation of [NiFe]-hydrogenase in E. coli is a complex process involving many steps and multiple accessory proteins. The two accessory proteins, HypA and HypB, interact with each other and are thought to cooperate to insert nickel into the active site of the hydrogenase-3 precursor protein. Both of these accessory proteins bind metal individually, but little is known about the metal-binding activities of the proteins once they assemble together into a functional complex. In this study, we investigate how complex formation modulates metal binding to the E. coli proteins HypA and HypB. This work lead to a re-evaluation of the HypA nickel affinity, revealing a KD on the order of 10−8 M. HypA can efficiently remove nickel, but not zinc, from the metal-binding site in the GTPase domain of HypB, a process that is less efficient when complex formation between HypA and HypB is disrupted. Furthermore, nickel release from HypB to HypA is specifically accelerated when HypB is loaded with GDP, but not GTP. These results are consistent with the HypA-HypB complex serving as a transfer step in the relay of nickel from membrane transporter to its final destination in the hydrogenase active site, and suggest that this complex contributes to the metal fidelity of this pathway. PMID:23899293

  18. Information Geometry of Complex Hamiltonians and Exceptional Points

    NASA Astrophysics Data System (ADS)

    Brody, Dorje; Graefe, Eva-Maria

    2013-08-01

    Information geometry provides a tool to systematically investigate parameter sensitivity of the state of a system. If a physical system is described by a linear combination of eigenstates of a complex (that is, non-Hermitian) Hamiltonian, then there can be phase transitions where dynamical properties of the system change abruptly. In the vicinities of the transition points, the state of the system becomes highly sensitive to the changes of the parameters in the Hamiltonian. The parameter sensitivity can then be measured in terms of the Fisher-Rao metric and the associated curvature of the parameter-space manifold. A general scheme for the geometric study of parameter-space manifolds of eigenstates of complex Hamiltonians is outlined here, leading to generic expressions for the metric.

  19. Knowledge Transfer on Complex Social Interventions in Public Health: A Scoping Study

    PubMed Central

    Dagenais, Christian; Malo, Marie; Robert, Émilie; Ouimet, Mathieu; Berthelette, Diane; Ridde, Valéry

    2013-01-01

    Objectives Scientific knowledge can help develop interventions that improve public health. The objectives of this review are (1) to describe the status of research on knowledge transfer strategies in the field of complex social interventions in public health and (2) to identify priorities for future research in this field. Method A scoping study is an exploratory study. After searching databases of bibliographic references and specialized periodicals, we summarized the relevant studies using a predetermined assessment framework. In-depth analysis focused on the following items: types of knowledge transfer strategies, fields of public health, types of publics, types of utilization, and types of research specifications. Results From the 1,374 references identified, we selected 26 studies. The strategies targeted mostly administrators of organizations and practitioners. The articles generally dealt with instrumental utilization and most often used qualitative methods. In general, the bias risk for the studies is high. Conclusion Researchers need to consider the methodological challenges in this field of research in order to improve assessment of more complex knowledge transfer strategies (when they exist), not just diffusion/dissemination strategies and conceptual and persuasive utilization. PMID:24324593

  20. Polarized radiative transfer in two-dimensional scattering medium with complex geometries by natural element method

    NASA Astrophysics Data System (ADS)

    Zhang, Yong; Kim, Yong-Jun; Yi, Hong-Liang; Xie, Ming; Tan, He-Ping

    2016-08-01

    The natural element method (NEM) is extended to solve the polarized radiative transfer problem in a two-dimensional scattering medium with complex geometries, in which the angular space is discretized by the discrete-ordinates approach, and the spatial discretization is conducted by the Galerkin weighted residuals approach. The Laplace interpolation scheme is adopted to obtain the shape functions used in the Galerkin weighted residuals approach. The NEM solution to the vector radiative transfer in a square enclosure filled with a Mie scattering medium is first examined to validate our program. We then study the polarized radiative transfer in two kinds of geometries filled with scattering medium which is equivalent to a suspension of latex spheres in water. Three sizes of spheres are considered. The results for non-dimensional polarized radiative flux along the boundaries and the angular distributions of the Stokes vector at specific positions are presented and discussed. For the complex geometry bounded by the square and circular object, numerical solutions are presented for the cases both with Lambertian (diffuse) reflection and with Fresnel reflection. Some interesting phenomenon are found and analyzed.

  1. Fluorescence energy-transfer studies on the pyruvate dehydrogenase complex isolated from Azotobacter vinelandii.

    PubMed

    Scouten, W H; De Graaf-Hess, A C; De Kok, A; Grande, H J; Visser, A J; Veeger, C

    1978-03-01

    Fluorescence energy transfer has been employed to estimate the minimum distance between each of the active sites of the 4 component enzymes of the pyruvate dehydrogenase multienzyme complex from Azotobacter vinelandii. No energy transfer was seen between thiochrome diphosphate, bound to the pyruvate decarboxylase active site, and the FAD of the lipoamide dehydrogenase active site. Likewise, several fluorescent sulfhydryl labels, which were specifically bound to the lipoyl moiety of lipoyl transacetylase, showed no energy transfer to either the flavin or thiochrome diphosphate. These observations suggest that all the active centers of the complex are quite far apart (greater than or equal to 40 nm), at least during some stages of catalysis. These results do not preclude the possibility that the distances change during catalysis. Several of the fluorescent probes used possessed multiple fluorescent lifetimes, as shown by determination of lifetime averages by both phase and modulation measurements on a phase fluorimeter. These lifetimes are shown to result from multiple factors, not necessarily related to multiple protein conformations. PMID:348464

  2. Hydrogen-Bound Complexes of Tropolone: Gateways for the Interrogation of Multiple Proton-Transfer Events

    NASA Astrophysics Data System (ADS)

    Nemchick, Deacon J.; Chew, Kathryn; Wolff, John E.; Vaccaro, Patrick H.

    2011-06-01

    Tropolone (TrOH) serves as a model system for the study of coherent proton-transfer processes, where a potential barrier of finite height hinders the symmetric exchange of a lone hydron between hydroxylic (proton-donating) and ketonic (proton-accepting) oxygen centers. This talk will discuss ongoing efforts to build upon the known structural and dynamical properties of tropolone so as to explore related multiple proton-transfer events that are mediated by successive formation and breaking of several hydrogen bonds. Of particular interest are weakly-bound complexes created in situ under ``cold'' molecular-beam conditions by docking amphoteric ligands (e.g., HF and HCOOH) into the reaction cleft of the TrOH substrate. Such species have the tantalizing possibility of undergoing double proton transfer, with resulting tunneling-induced bifurcation of rovibronic features reflecting the intrinsic vibrational and/or electronic specificity of the attendant unimolecular transformation. Spectroscopic studies of several hydrogen-bound TrOH complexes through use of the richly structured tilde{A}1B2-tilde{X}1A1 (π *← π ) absorption system will be presented, with complementary quantum-chemical calculations serving to guide the assignment and interpretation of observed spectral patterns. L. A. Burns, D. Murdock, and P. H. Vaccaro, Mol. Phys., 108, 1171 (2010).

  3. Concerted or stepwise hydrogen transfer in the transfer hydrogenation of acetophenone catalyzed by ruthenium-acetamido complex: a theoretical mechanistic investigation.

    PubMed

    Guo, Xiaojia; Tang, Yanhui; Zhang, Xin; Lei, Ming

    2011-11-10

    In this paper, the mechanism of transfer hydrogenation of acetophenone catalyzed by ruthenium-acetamido complex was studied using density function theory (DFT) method. The catalytic cycle of transfer hydrogenation consists of hydrogen transfer (HT) step and dehydrogenation (DH) step of isopropanol (IPA). Inner sphere mechanism (paths 1 and 7) and outer sphere mechanism (paths 2-6) in HT step are fully investigated. Calculated results indicate that DH step of IPA (from (i)1 to (i)2) is the rate-determining step in the whole catalytic cycle, which has a potential energy barrier of 16.2 kcal/mol. On the other hand, the maximum potential energy barriers of paths 1-7 in the HT step are 5.9, 12.7, 24.4, 16.8, 23.7, 7.2, and 6.1 kcal/mol, respectively. The inner sphere pathways (paths 1 and 7) are favorable hydrogen transfer modes compared with outer sphere pathways, and the proton transferred to the oxygen atom of acetophenone comes from the hydroxyl group but not from amino group of acetamido ligand. Those theoretical results are in agreement with experimental report. However, in view of this DFT study in the inner sphere mechanism of HT step, hydride transfer and proton transfer are concerted and asynchronous hydrogen transfer but not a stepwise one, and hydride transfer precedes proton transfer in this case. PMID:21974747

  4. Transfer of Flexibility between Ankyrin Repeats in IκBα upon Formation of the NF-κB Complex

    PubMed Central

    Sue, Shih-Che; Cervantes, Carla; Komives, Elizabeth A.; Dyson, H. Jane

    2008-01-01

    The mechanism of inhibition of the transcriptional activator nuclear factor-kappaB (NF-κB) by the inhibitor IκBα is central to the understanding of the control of transcriptional activity via this widely-employed pathway. Previous studies suggested that IκBα, a modular protein with an NF-κB binding domain consisting of 6 ankyrin repeat domains (ANK), shows differential flexibility, with ANK 1-4 apparently more rigid in solution in the absence of NF-κB than ANK 5 and 6. Here we report NMR studies that confirm the enhanced flexibility of ANK 5 and 6 in free IκBα. Upon binding of NF-κB, ANK 5 and 6 become well-structured and rigid, but, somewhat surprisingly, other domains of the IκBα, which were relatively rigid in the free protein, become significantly more flexible. Due to the high molecular weights of the component proteins and the complexes, we employ a hierarchical experimental plan to maximize the available information on local flexibility in the ankyrin repeat domains. Backbone resonances of the 221-residue IκBα protein were assigned firstly in a smaller construct consisting of ankyrin repeats 1-4. These assignments could be readily transferred to the spectra of the construct containing 6 repeats, both free and complexed with various combinations of the NF-κB p50 and p65 domains. TROSY-type NMR experiments on differentially-labeled proteins enabled information on backbone structure and dynamics to be obtained, even in complexes with molecular weights approaching 100 kDa. Changes in the flexibility and stability of the various ankyrin repeat domains of IκBα complex formation takes a variety of forms depending on the position of the domain in the complex, providing a variety of examples of the structural and functional utility of intrinsically-unstructured or partly folded protein domains. PMID:18565540

  5. Investigation of ground state charge transfer complex between paracetamol and p-chloranil through DFT and UV-visible studies

    NASA Astrophysics Data System (ADS)

    Shukla, Madhulata; Srivastava, Nitin; Saha, Satyen

    2012-08-01

    The present report deals with the theoretical investigation on ground state structure and charge transfer (CT) transitions in paracetamol (PA)/p-chloranil (CA) complex using Density Functional Theory (DFT) and Time Dependent Density Functional Theory (TD-DFT) method. It is found that Cdbnd O bond length of p-chloranil increases on complexation with paracetamol along with considerable amount of charge transfer from PA to CA. TD-DFT calculations have been performed to analyse the observed UV-visible spectrum of PA-CA charge transferred complex. Interestingly, in addition to expected CT transition, a weak symmetry relieved π-π* transition in the chloranil is also observed.

  6. Information transfer in verbal presentations at scientific meetings

    NASA Astrophysics Data System (ADS)

    Flinn, Edward A.

    The purpose of this note is to suggest a quantitative approach to deciding how much time to give a speaker at a scientific meeting. The elementary procedure is to use the preacher's rule of thumb that no souls are saved after the first 20 minutes. This is in qualitative agreement with the proverb that one cannot listen to a single voice for more than an hour without going to sleep. A refinement of this crude approach can be made by considering the situation from the point of view of a linear physical system with an input, a transfer function, and an output. We attempt here to derive an optimum speaking time through these considerations.

  7. Second law of information thermodynamics with entanglement transfer.

    PubMed

    Tajima, Hiroyasu

    2013-10-01

    We present an inequality which holds in the thermodynamical processes with measurement and feedback controls and uses only the Helmholtz free energy and the entanglement of formation: W(ext)≤-ΔF-k(B)TΔE(F). The quantity -ΔE(F), which is positive, expresses the amount of entanglement transfer from system S to probe P through the interaction U(SP) during the measurement. It is easier to achieve the upper bound in this inequality than in the Sagawa-Ueda inequality [Phys. Rev. Lett. 100, 080403 (2008)]. Our inequality has clear physical meaning: in the above thermodynamical processes, the work which we can extract from the thermodynamic system is greater than the upper bound in the conventional thermodynamics by the amount of the entanglement extracted by the measurement. PMID:24229151

  8. Enhanced Electron-Transfer Reactivity of Nonheme Manganese(IV)– Oxo Complexes by Binding Scandium Ions

    PubMed Central

    Yoon, Heejung; Lee, Yong-Min; Wu, Xiujuan; Cho, Kyung-Bin; Sarangi, Ritimukta

    2014-01-01

    One and two scandium ions (Sc3+) are bound strongly to nonheme manganese(IV)–oxo complexes, [(N4Py)MnIV(O)]2+ (N4Py = N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine) and [(Bn-TPEN)MnIV(O)]2+ (Bn-TPEN = N-benzyl-N,N′,N′-tris(2-pyridylmethyl)-1,2-diaminoethane), to form MnIV(O)–(Sc3+)1 and MnIV(O)–(Sc3+)2 complexes, respectively. The binding of Sc3+ ions to the MnIV(O) complexes was examined by spectroscopic methods as well as by DFT calculations. The one-electron reduction potentials of the MnIV(O) complexes were markedly shifted to a positive direction by binding of Sc3+ ions. Accordingly, rates of the electron transfer reactions of the MnIV(O) complexes were enhanced as much as 107–fold by binding of two Sc3+ ions. The driving force dependence of electron transfer from various electron donors to the MnIV(O) and MnIV(O)–(Sc3+)2 complexes was examined and analyzed in light of the Marcus theory of electron transfer to determine the reorganization energies of electron transfer. The smaller reorganization energies and much more positive reduction potentials of the MnIV(O)–(Sc3+)2 complexes resulted in remarkable enhancement of the electron-transfer reactivity of the MnIV(O) complexes. Such a dramatic enhancement of the electron-transfer reactivity of the MnIV(O) complexes by binding of Sc3+ ions resulted in the change of mechanism in the sulfoxidation of thioanisoles by MnIV(O) complexes from a direct oxygen atom transfer pathway without metal ion binding to an electron-transfer pathway with binding of Sc3+ ions. PMID:23742163

  9. Analytical studies on the charge transfer complexes of loperamide hydrochloride and trimebutine drugs. Spectroscopic and thermal characterization of CT complexes.

    PubMed

    Elqudaby, Hoda M; Mohamed, Gehad G; El-Din, Ghada M G

    2014-08-14

    Charge transfer complexes of loperamide hydrochloride (LOP.HCl) and trimebutine (TB) drugs as electron donor with 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ), tetracyanoethylene (TCNE) and 7,7,8,8-tetracyanoquinodimethane (TCNQ) as π-acceptors in acetonitrile were investigated spectrophotometrically to determine the cited drugs in pure and dosage forms. The reaction gives highly coloured complex species which are measured spectrophotometrically at 460, 415 and 842nm in case of LOP.HCl and at 455, 414 and 842nm in case of TB using DDQ, TCNE and TCNQ reagents, respectively. The optimum experimental conditions have been studied carefully and optimized. Beer's law was obeyed over the concentration ranges of 47.70-381.6, 21.50-150.5 and 10.00-100.0μgmL(-1) for LOP.HCl and 37.85-264.9, 38.75-310.0 and 7.75-155.0μgmL(-1) for TB using DDQ, TCNE and TCNQ reagents, respectively. Sandell sensitivity, standard deviation, relative standard deviation, limit of detection and quantification were calculated. The obtained data refer to high accuracy and precision of the proposed method. These results are also confirmed by inter and intra-day precision with percent recovery of 99.18-101.1% and 99.32-101.4% in case of LOP.HCl and 98.00-102.0% and 97.50-101.4% in case of TB using DDQ, TCNE and TCNQ reagents for intra- and inter-day, respectively. These data were compared with those obtained using official methods for the determination of the cited drugs. The stability constants of the CT complexes were determined. The final products of the reaction were isolated and characterized using FT-IR, (1)H NMR, elemental analysis and thermogravimetric analysis (TG). The stoichiometry and apparent formation constant of the complexes formed were determined by applying the conventional spectrophotometric molar ratio method. PMID:24727166

  10. Tactile information processing in the trigeminal complex of the rat

    NASA Astrophysics Data System (ADS)

    Pavlov, Alexey N.; Tupitsyn, Anatoly N.; Makarov, Valery A.; Panetsos, Fivos; Moreno, Angel; Garcia-Gonzalez, Victor; Sanchez-Jimenez, Abel

    2007-02-01

    We study mechanisms of information processing in the principalis (Pr5), oralis (Sp5o) and interpolaris (Sp5i) nuclei of the trigeminal sensory complex of the rat under whisker stimulation by short air puffs. After the standard electrophysiological description of the neural spiking activity we apply a novel wavelet based method quantifying the structural stability of firing patterns evoked by a periodic whisker stimulation. We show that the response stability depends on the puff duration delivered to the vibrissae and differs among the analyzed nuclei. Pr5 and Sp5i exhibit the maximal stability to an intermediate stimulus duration, whereas Sp5o shows "preference" for short stimuli.

  11. Specificity, promiscuity, and the structure of complex information processing networks

    NASA Astrophysics Data System (ADS)

    Myers, Christopher

    2006-03-01

    Both the top-down designs of engineered systems and the bottom-up serendipities of biological evolution must negotiate tradeoffs between specificity and control: overly specific interactions between components can make systems brittle and unevolvable, while more generic interactions can require elaborate control in order to aggregate specificity from distributed pieces. Complex information processing systems reveal network organizations that navigate this landscape of constraints: regulatory and signaling networks in cells involve the coordination of molecular interactions that are surprisingly promiscuous, and object-oriented design in software systems emphasizes the polymorphic composition of objects of minimal necessary specificity [C.R. Myers, Phys Rev E 68, 046116 (2003)]. Models of information processing arising both in systems biology and engineered computation are explored to better understand how particular network organizations can coordinate the activity of promiscuous components to achieve robust and evolvable function.

  12. Management of complex immunogenetics information using an enhanced relational model.

    PubMed

    Barsalou, T; Sujansky, W; Herzenberg, L A; Wiederhold, G

    1991-10-01

    Flow cytometry has become a technique of paramount importance in the armamentarium of the scientist in such domains as immunogenetics. In the PENGUIN project, we are currently developing the architecture for an expert database system to facilitate the design of flow-cytometry experiments. This paper describes the core of this architecture--a methodology for managing complex biomedical information in an extended relational framework. More specifically, we exploit a semantic data model to enhance relational databases with structuring and manipulation tools that take more domain information into account and provide the user with an appropriate level of abstraction. We present specific applications of the structural model to database schema management, data retrieval and browsing, and integrity maintenance. PMID:1743006

  13. [Palliative care at home, transferring information to emergency medical teams].

    PubMed

    Ribeaucoup, Luc; Roche, Blandine

    2015-11-01

    Many people wish to die at home. However, the end-of-life period can be marked by the occurrence of numerous symptoms causing situations of crisis. Emergency medical teams are therefore frequently called upon. In order to be able to make the right decisions in a short space of time, they must have quick access to all the relevant information. PMID:26567076

  14. A diabatic state model for double proton transfer in hydrogen bonded complexes

    SciTech Connect

    McKenzie, Ross H.

    2014-09-14

    Four diabatic states are used to construct a simple model for double proton transfer in hydrogen bonded complexes. Key parameters in the model are the proton donor-acceptor separation R and the ratio, D{sub 1}/D{sub 2}, between the proton affinity of a donor with one and two protons. Depending on the values of these two parameters the model describes four qualitatively different ground state potential energy surfaces, having zero, one, two, or four saddle points. Only for the latter are there four stable tautomers. In the limit D{sub 2} = D{sub 1} the model reduces to two decoupled hydrogen bonds. As R decreases a transition can occur from a synchronous concerted to an asynchronous concerted to a sequential mechanism for double proton transfer.

  15. The structure of control and data transfer management system for the GAMMA-400 scientific complex

    NASA Astrophysics Data System (ADS)

    Arkhangelskiy, A. I.; Bobkov, S. G.; Serdin, O. V.; Gorbunov, M. S.; Topchiev, N. P.

    2016-02-01

    A description of the control and data transfer management system for scientific instrumentation involved in the GAMMA-400 space project is given. The technical capabilities of all specialized equipment to provide the functioning of the scientific instrumentation and satellite support systems are unified in a single structure. Control of the scientific instruments is maintained using one-time pulse radio commands, as well as program commands in the form of 16-bit code words, which are transmitted via onboard control system and scientific data acquisition system. Up to 100 GByte of data per day can be transferred to the ground segment of the project. The correctness of the proposed and implemented structure, engineering solutions and electronic elemental base selection has been verified by the experimental working-off of the prototype of the GAMMA-400 scientific complex in laboratory conditions.

  16. Probing the Förster resonance energy transfer between fluorescent copper nanoclusters and cobalt complex

    NASA Astrophysics Data System (ADS)

    Patel, Arun Singh; Sahoo, Harekrushna; Mohanty, Tanuja

    2014-08-01

    In the present study, we report the Förster resonance energy transfer (FRET) from fluorescent copper nanoclusters (Cu NCs) as donor to cobalt complex (nitrate (Co (NO3)2)) as acceptor. Fluorescent Cu NCs have been synthesized on bovine serum albumin template by wet chemistry method; these NCs show fluorescence maxima at 435 nm. The fluorescence intensity of Cu NCs is quenched in proximity presence of acceptors, and subsequently, energy is transferred. In such type of system, these Cu NCs are found to be efficient donor with Förster distance (R0) 8.9 Å and FRET efficiency (E) up to 42%. The Förster distance obtained is found to be the lowest among other reported values for donor/acceptor pair till today.

  17. Proton transfer induced by receding water in Glycine---(Water)2 Complex

    NASA Astrophysics Data System (ADS)

    Pathak, Rajeev

    2011-03-01

    We investigate molecular co-operativity in the zwitterionic configuration of Glycine (Gly) with two proximal water molecules, Gly---(Water)2 , by deliberately making one of the water molecules recede from the remaining complex. The consequent intra-molecular proton transfer that renders the zwitterionic configuration into a neutral one is viewed under two scalar field descriptors: Molecular Electrostatic Potential (MESP), reflecting the modifications in the environment and the HOMO (highest occupied molecular orbital) electron density. We quantify the process further by energetics, through a many-body analysis of the interaction energy as well as salient IR spectral signatures associated with the proton-transfer. While we employ the decent MP2/aug-cc-pvDZ level of theory to seek optimal structures, it is gratifying that a prescription within density functional theory (DFT) also provides a reliable description of this process.

  18. Photocurrent generation through charge-transfer processes in noncovalent perylenediimide/DNA complexes.

    PubMed

    Takada, Tadao; Ido, Misa; Ashida, Akane; Nakamura, Mitsunobu; Fujitsuka, Mamoru; Kawai, Kiyohiko; Majima, Tetsuro; Yamana, Kazushige

    2015-04-27

    The charge-transfer process in noncovalent perylenediimide (PDI)/DNA complexes has been investigated by using nanosecond laser flash photolysis (LFP) and photocurrent measurements. The PDI/DNA complexes were prepared by inclusion of cationic PDI molecules into the artificial cavities created inside DNA. The LFP experiments showed that placement of the PDI chromophore at a specific site and included within the base stack of DNA led to the efficient generation of a charge-separated state with a long lifetime by photoexcitation. When two PDI chromophores were separately placed at different positions in DNA, the yield of the charge-separated state with a long lifetime was dependent upon the number of A-T base pairs between the PDIs, which was explained by electron hopping from one PDI to another. Photocurrent generation of the DNA-modified electrodes with the complex was also dependent upon the arrangement of the PDI chromophores. A good correlation was obtained between observed charge separation and photocurrent generation on the PDI/DNA-modified electrodes, which demonstrated the importance of the defined arrangement and assembly of organic chromophores in DNA for efficient charge separation and transfer in multichromophore arrays. PMID:25784217

  19. Lateral gene transfer of an ABC transporter complex between major constituents of the human gut microbiome

    PubMed Central

    2012-01-01

    Background Several links have been established between the human gut microbiome and conditions such as obesity and inflammatory bowel syndrome. This highlights the importance of understanding what properties of the gut microbiome can affect the health of the human host. Studies have been undertaken to determine the species composition of this microbiome and infer functional profiles associated with such host properties. However, lateral gene transfer (LGT) between community members may result in misleading taxonomic attributions for the recipient organisms, thus making species-function links difficult to establish. Results We identified a peptides/nickel transport complex whose components differed in abundance based upon levels of host obesity, and assigned the encoded proteins to members of the microbial community. Each protein was assigned to several distinct taxonomic groups, with moderate levels of agreement observed among different proteins in the complex. Phylogenetic trees of these proteins produced clusters that differed greatly from taxonomic attributions and indicated that habitat-directed LGT of this complex is likely to have occurred, though not always between the same partners. Conclusions These findings demonstrate that certain membrane transport systems may be an important factor within an obese-associated gut microbiome and that such complexes may be acquired several times by different strains of the same species. Additionally, an example of individual proteins from different organisms being transferred into one operon was observed, potentially demonstrating a functional complex despite the donors of the subunits being taxonomically disparate. Our results also highlight the potential impact of habitat-directed LGT on the resident microbiota. PMID:23116195

  20. Synthesis and structures of ruthenium–NHC complexes and their catalysis in hydrogen transfer reaction

    PubMed Central

    Chen, Chao; Lu, Chunxin; Zheng, Qing; Zhang, Min

    2015-01-01

    Summary Ruthenium complexes [Ru(L1)2(CH3CN)2](PF6)2 (1), [RuL1(CH3CN)4](PF6)2 (2) and [RuL2(CH3CN)3](PF6)2 (3) (L1= 3-methyl-1-(pyrimidine-2-yl)imidazolylidene, L2 = 1,3-bis(pyridin-2-ylmethyl)benzimidazolylidene) were obtained through a transmetallation reaction of the corresponding nickel–NHC complexes with [Ru(p-cymene)2Cl2]2 in refluxing acetonitrile solution. The crystal structures of three complexes determined by X-ray analyses show that the central Ru(II) atoms are coordinated by pyrimidine- or pyridine-functionalized N-heterocyclic carbene and acetonitrile ligands displaying the typical octahedral geometry. The reaction of [RuL1(CH3CN)4](PF6)2 with triphenylphosphine and 1,10-phenanthroline resulted in the substitution of one and two coordinated acetonitrile ligands and afforded [RuL1(PPh3)(CH3CN)3](PF6)2 (4) and [RuL1(phen)(CH3CN)2](PF6)2 (5), respectively. The molecular structures of the complexes 4 and 5 were also studied by X-ray diffraction analysis. These ruthenium complexes have proven to be efficient catalysts for transfer hydrogenation of various ketones. PMID:26664598

  1. Physical characteristics of lanthanide complexes that act as magnetization transfer (MT) contrast agents

    NASA Astrophysics Data System (ADS)

    Zhang, Shanrong; Sherry, A. Dean

    2003-02-01

    Rapid water exchange is normally considered a prerequisite for efficient Gd 3+-based MRI contrast agents. Yet recent measures of exchange rates in some Gd 3+ complexes have shown that water exchange can become limiting when such complexes are attached to larger macromolecular structures. A new class of lanthanide complexes that display unusually slow water exchange (bound water lifetimes ( τM298) > 10 μs) has recently been reported. This apparent disadvantage may be taken advantage of by switching the metal ion from gadolinium(III) to a lanthanide that shifts the bound water resonance substantially away from bulk water. Given appropriate water exchange kinetics, one can then alter the intensity of the bulk water signal by selective presaturation of this highly shifted, Ln3+-bound water resonance. This provides the basis of a new method to alter MR image contrast in tissue. We have synthesized a variety of DOTA-tetra(amide) ligands to evaluate as potential magnetization transfer (MT) contrast agents and found that the bound water lifetimes in these complexes are sensitive to both ligand structure (a series of Eu 3+ complexes have τM298 values that range from 1 to 1300 μs) and the identity of the paramagnetic Ln3+ cation (from 3 to 800 μs for a single ligand). This demonstrates that it may be possible either to fine-tune the ligand structure or to select proper lanthanide cation to create an optimal MT agent for any clinical imaging field.

  2. Electronic and vibronic properties of a discotic liquid-crystal and its charge transfer complex

    SciTech Connect

    Haverkate, Lucas A.; Mulder, Fokko M.; Zbiri, Mohamed Johnson, Mark R.; Carter, Elizabeth; Kotlewski, Arek; Picken, S.

    2014-01-07

    Discotic liquid crystalline (DLC) charge transfer (CT) complexes combine visible light absorption and rapid charge transfer characteristics, being favorable properties for photovoltaic (PV) applications. We present a detailed study of the electronic and vibrational properties of the prototypic 1:1 mixture of discotic 2,3,6,7,10,11-hexakishexyloxytriphenylene (HAT6) and 2,4,7-trinitro-9-fluorenone (TNF). It is shown that intermolecular charge transfer occurs in the ground state of the complex: a charge delocalization of about 10{sup −2} electron from the HAT6 core to TNF is deduced from both Raman and our previous NMR measurements [L. A. Haverkate, M. Zbiri, M. R. Johnson, B. Deme, H. J. M. de Groot, F. Lefeber, A. Kotlewski, S. J. Picken, F. M. Mulder, and G. J. Kearley, J. Phys. Chem. B 116, 13098 (2012)], implying the presence of permanent dipoles at the donor-acceptor interface. A combined analysis of density functional theory calculations, resonant Raman and UV-VIS absorption measurements indicate that fast relaxation occurs in the UV region due to intramolecular vibronic coupling of HAT6 quinoidal modes with lower lying electronic states. Relatively slower relaxation in the visible region the excited CT-band of the complex is also indicated, which likely involves motions of the TNF nitro groups. The fast quinoidal relaxation process in the hot UV band of HAT6 relates to pseudo-Jahn-Teller interactions in a single benzene unit, suggesting that the underlying vibronic coupling mechanism can be generic for polyaromatic hydrocarbons. Both the presence of ground state CT dipoles and relatively slow relaxation processes in the excited CT band can be relevant concerning the design of DLC based organic PV systems.

  3. Uridine insertion/deletion editing in trypanosomes: a playground for RNA-guided information transfer.

    PubMed

    Aphasizhev, Ruslan; Aphasizheva, Inna

    2011-01-01

    RNA editing is a collective term referring to enzymatic processes that change RNA sequence apart from splicing, 5' capping or 3' extension. In this article, we focus on uridine insertion/deletion mRNA editing found exclusively in mitochondria of kinetoplastid protists. This type of editing corrects frameshifts, introduces start and stops codons, and often adds much of the coding sequence to create an open reading frame. The mitochondrial genome of trypanosomatids, the most extensively studied clade within the order Kinetoplastida, is composed of ∼50 maxicircles with limited coding capacity and thousands of minicircles. To produce functional mRNAs, a multitude of nuclear-encoded factors mediate interactions of maxicircle-encoded pre-mRNAs with a vast repertoire of minicircle-encoded guide RNAs. Editing reactions of mRNA cleavage, U-insertions or U-deletions, and ligation are catalyzed by the RNA editing core complex (RECC, the 20S editosome) while each step of this enzymatic cascade is directed by guide RNAs. These 50-60 nucleotide (nt) molecules are 3' uridylated by RET1 TUTase and stabilized via association with the gRNA binding complex (GRBC). Remarkably, the information transfer between maxicircle and minicircle transcriptomes does not rely on template-dependent polymerization of nucleic acids. Instead, intrinsic substrate specificities of key enzymes are largely responsible for the fidelity of editing. Conversely, the efficiency of editing is enhanced by assembling enzymes and RNA binding proteins into stable multiprotein complexes. WIREs RNA 2011 2 669-685 DOI: 10.1002/wrna.82 For further resources related to this article, please visit the WIREs website. PMID:21823228

  4. Transferring information through a mixed-five-spin chain channel

    NASA Astrophysics Data System (ADS)

    Arian Zad, Hamid; Movahhedian, Hossein

    2016-08-01

    We initially introduce one-dimensional mixed-five-spin chain with Ising-XY model which includes mixture of spins-1/2 and spins-1. Here, it is considered that nearest spins (1,1/2) have Ising-type interaction and nearest spins (1/2,1/2) have both XY-type and Dzyaloshinskii–Moriya (DM) interactions together. Nearest spins (1,1) have XX Heisenberg interaction. This system is in the vicinity of an external homogeneous magnetic field B in thermal equilibrium state. We promote the quantum information transmitting protocol verified for a normal spin chain with simple model (refer to Rossini D, Giovannetti V and Fazio R 2007 Int. J. Quantum Infor. 5 439) (widely in reference: Giovannetti V and Fazio R 2005 Phys. Rev. A 71 032314) by means of considering the suggested mixed-five-spin chain as a quantum communication channel for transmitting both qubits and qutrits ideally. Hence, we investigate some useful quantities such as quantum capacity and quantum information transmission rate for the system. Finally, we conclude that, when the DM interaction between spins (1/2,1/2) increases the system is a more ideal channel for transmitting information.

  5. Measurement and Information Extraction in Complex Dynamics Quantum Computation

    NASA Astrophysics Data System (ADS)

    Casati, Giulio; Montangero, Simone

    Quantum Information processing has several di.erent applications: some of them can be performed controlling only few qubits simultaneously (e.g. quantum teleportation or quantum cryptography) [1]. Usually, the transmission of large amount of information is performed repeating several times the scheme implemented for few qubits. However, to exploit the advantages of quantum computation, the simultaneous control of many qubits is unavoidable [2]. This situation increases the experimental di.culties of quantum computing: maintaining quantum coherence in a large quantum system is a di.cult task. Indeed a quantum computer is a many-body complex system and decoherence, due to the interaction with the external world, will eventually corrupt any quantum computation. Moreover, internal static imperfections can lead to quantum chaos in the quantum register thus destroying computer operability [3]. Indeed, as it has been shown in [4], a critical imperfection strength exists above which the quantum register thermalizes and quantum computation becomes impossible. We showed such e.ects on a quantum computer performing an e.cient algorithm to simulate complex quantum dynamics [5,6].

  6. Bis(pentamethylcyclopentadienyl) ytterbium: Electron-transfer reactions with organotransition metal complexes

    SciTech Connect

    Matsunaga, P.T.

    1991-11-01

    The divalent lanthanide complex, (Me{sub 5}C{sub 5}){sub 2}Yb, reacts with methylcopper to produce the base-free, ytterbium-methyl complex, (Me{sub 5}C{sub 5}){sub 2}YbMe. This product forms a asymmetric, methyl-bridged dimer in the solid state. The bulky alkyl complex, (Me{sub 5}C{sub 5}){sub 2}YbCH(SiMe{sub 3}){sub 2}, displays similar chemistry to (Me{sub 5}C{sub 5}){sub 2}YbMe, but at a reduced reaction rate due to the limited accessibility of the metal in (Me{sub 5}C{sub 5}){sub 2}YbCH(SiMe{sub 3}){sub 2}. Copper and silver halide salts react with (Me{sub 5}C{sub 5}){sub 2}V to produce the trivalent halide derivatives, (Me{sub 5}C{sub 5}){sub 2}VX (X + F, Cl, Br, I). The chloride complex, (Me{sub 5}C{sub 5}){sub 2}VCl, reacts with lithium reagents to form the phenyl and borohydride species. Nitrous oxide transfers an oxygen atom to (Me{sub 5}C{sub 5}){sub 2}V producing the vanadium-oxo complex, (Me{sub 5}Ce{sub 5}){sub 2}VO. The trivalent titanium species, (Me{sub 5}C{sub 5}){sub 2}TiX (X = Cl, Br, Me, BH{sub 4}), form bimetallic coordination complexes with (Me{sub 5}C{sub 5}){sub 2}Yb. The magnetic behavior of the products indicates that electron transfer has not occurred. The solid state structures of the chloride and bromide complexes show unusual bend angles for the halide bridges between ytterbium and titanium. A model based on frontier orbital theory has been proposed to account for the bending behavior in these species. The bimetallic methyl complex contains a linear methyl bridge between ytterbium and titanium.

  7. Energy transfer from conjugated polymer to bacterial light-harvesting complex

    NASA Astrophysics Data System (ADS)

    Buczynska, D.; Bujak, Ł.; Loi, M. A.; Brotosudarmo, T. H. P.; Cogdell, R.; Mackowski, S.

    2012-10-01

    Energy transfer from a conjugated polymer blend (poly(9,9-dioctylfluorenyl-2,7-diyl):poly (2-methoxy-5-(2-ethylhexyloxy)-1, 4-phenylenevinylene) to a light-harvesting complex 2 from purple bacteria has been demonstrated using time-resolved fluorescence spectroscopy. For our hybrid nanostructure, we observe a 30% reduction of the fluorescence lifetime of the polymer emission as compared to the pure polymer layer. This result is an important step towards integrating naturally evolved biomolecules with synthetic materials into biohybrid organic electronic systems.

  8. Formation of charge-transfer-complex in organic:metal oxides systems

    NASA Astrophysics Data System (ADS)

    Wu, S. P.; Kang, Y.; Liu, T. L.; Jin, Z. H.; Jiang, N.; Lu, Z. H.

    2013-04-01

    It is found that composite systems consisting of 4,4'-bis(carbazol-9-yl)biphenyl (CBP) and molybdenum trioxide (MoO3) form an IR absorption band around 847 nm. It is also found that the vibrational modes of the CBP, as measured by Fourier Transform Infrared Spectroscopy, are quenched upon the formation of charge-transfer-complex (CTC) between CBP and MoO3. By examining several sets of organic:metal oxides systems, we discovered that the IR absorption band of the CTCs follow two distinct mechanisms depending on the nature and location of the HOMOs in the organic molecules.

  9. Charge separation and energy transfer in the photosystem II core complex studied by femtosecond midinfrared spectroscopy.

    PubMed

    Pawlowicz, N P; Groot, M-L; van Stokkum, I H M; Breton, J; van Grondelle, R

    2007-10-15

    The core of photosystem II (PSII) of green plants contains the reaction center (RC) proteins D1D2-cytb559 and two core antennas CP43 and CP47. We have used time-resolved visible pump/midinfrared probe spectroscopy in the region between 1600 and 1800 cm(-1) to study the energy transfer and charge separation events within PSII cores. The absorption difference spectra in the region of the keto and ester chlorophyll modes show spectral evolution with time constants of 3 ps, 27 ps, 200 ps, and 2 ns. Comparison of infrared (IR) difference spectra obtained for the isolated antennas CP43 and CP47 and the D1D2-RC with those measured for the PSII core allowed us to identify the features specific for each of the PSII core components. From the presence of the CP43 and CP47 specific features in the spectra up to time delays of 20-30 ps, we conclude that the main part of the energy transfer from the antennas to the RC occurs on this timescale. Direct excitation of the pigments in the RC evolution associated difference spectra to radical pair formation of PD1+PheoD1- on the same timescale as multi-excitation annihilation and excited state equilibration within the antennas CP43 and CP47, which occur within approximately 1-3 ps. The formation of the earlier radical pair ChlD1+PheoD1-, as identified in isolated D1D2 complexes with time-resolved mid-IR spectroscopy is not observed in the current data, probably because of its relatively low concentration. Relaxation of the state PD1+PheoD1-, caused by a drop in free energy, occurs in 200 ps in closed cores. We conclude that the kinetic model proposed earlier for the energy and electron transfer dynamics within the D1D2-RC, plus two slowly energy-transferring antennas C43 and CP47 explain the complex excited state and charge separation dynamics in the PSII core very well. We further show that the time-resolved IR-difference spectrum of PD1+PheoD1- as observed in PSII cores is virtually identical to that observed in the isolated D1D2-RC

  10. New ruthenium nitrosyl pincer complexes bearing an O2 ligand. Mono-oxygen transfer.

    PubMed

    Fogler, Eran; Efremenko, Irena; Gargir, Moti; Leitus, Gregory; Diskin-Posner, Yael; Ben-David, Yehoshoa; Martin, Jan M L; Milstein, David

    2015-03-01

    We report on Ru((II))(μ(2)-O2) nitrosyl pincer complexes that can return to their original Ru(0) state by reaction with mono-oxygen scavengers. Potential intermediates were calculated by density functional theory (DFT) and a mechanism is proposed, revealing a new type of metal-ligand cooperation consisting of activation of the O2 moiety by both the metal center and the NO ligand. Reaction of the Ru(0) nitrosyl complex 1 with O2 quantitatively yielded the crystallographically characterized Ru((II)) (μ(2)-O2) nitrosyl complex 2. Reaction of 2 with the mono-oxygen scavengers phosphines or CO gave the Ru(0) complex 1 and phosphine oxides, or the carbonyl complex 3 (1 trapped by CO) and CO2, respectively. Reaction of 2 with 1 equiv of phosphine at room temperature or -40 °C resulted in immediate formation of half an equivalent of 1 and 1 equiv of phosphine oxide, while half an equivalent of 2 remained unchanged. Overnight reaction at room temperature of 2 with excess CO (≥3 equiv) resulted in 3 and CO2 gas as the only products. Reaction of 1 with 1 equiv of mono-oxygen source (dioxirane) at -78 °C yielded the Ru((II))(μ(2)-O2) complex 2. Similarly, reaction of the Ru(0) dearomatized complex 4 with O2 led to the crystallographicaly characterized Ru((II))(μ(2)-O2) complex 5. Further reaction of 5 with mono-oxygen scavengers (phosphines or CO) led to the Ru(0) complex 4 and phosphine oxides or complex 6 (4 trapped by CO) and CO2. When instead only 1 equiv of 5 was reacted with 1 equiv of phosphine at room temperature, immediate formation of half an equivalent of 4 and 1 equiv of phosphine oxide took place, while half an equivalent of 5 remained unchanged. When 5 reacted with an excess of CO (≥3 equiv), complex 6 and CO2 gas were the only products obtained. DFT studies indicate a new mode of metal-ligand cooperation involving the nitrosyl ligand in the oxygen transfer process. PMID:25695626

  11. Morphology-Induced Information Transfer in Bat Sonar

    NASA Astrophysics Data System (ADS)

    Reijniers, Jonas; Vanderelst, Dieter; Peremans, Herbert

    2010-10-01

    It has been argued that an important part of understanding bat echolocation comes down to understanding the morphology of the bat sound processing apparatus. In this Letter we present a method based on information theory that allows us to assess target localization performance of bat sonar, without a priori knowledge on the position, size, or shape of the reflecting target. We demonstrate this method using simulated directivity patterns of the frequency-modulated bat Micronycteris microtis. The results of this analysis indicate that the morphology of this bat’s sound processing apparatus has evolved to be a compromise between sensitivity and accuracy with the pinnae and the noseleaf playing different roles.

  12. Charge-transfer complexation and photoreduction of viologen derivatives bearing the para-substituted benzophenone group in dimethyl sulfoxide

    SciTech Connect

    Tanaka, Chiho; Nambu, Yoko; Endo, Takeshi

    1992-08-20

    New viologen derivatives having the various para-substituted benzophenone groups connected with a -(CH{sub 2}){sub 3}-linkage were effectively photoreduced by dimethyl sulfoxide by the intramolecular charge transfer complex formation between the viologen and benzophenone groups through effective stacking. The photoreduction was enhanced by the introduction of electron-donating para-substituents on the benzophenone units which were favorable for the intramolecular charge transfer complexation. 6 refs., 5 figs.

  13. Ultrafast photoinduced dynamics of halogenated cyclopentadienes: observation of geminate charge-transfer complexes in solution.

    PubMed

    Wolf, T J A; Schalk, O; Radloff, R; Wu, G; Lang, P; Stolow, A; Unterreiner, A-N

    2013-05-14

    The photoinduced dynamics of the fully halogenated cyclopentadienes C5Cl6 and C5Br6 have been investigated in solution and gas phase by femtosecond time-resolved spectroscopy. Both in solution and in gas phase, homolytic dissociation into a halogen radical and a C5X5 (X = Cl, Br) radical was observed. In liquid phase, solvent-dependent formation of charge transfer complexes between geminate radicals was observed for the first time. These complexes were found to be surprisingly stable and offered the opportunity to follow the dynamics of specific radical pairs. In the case of C5Cl6 in trichloroethanol, a reaction of the chlorine radical with molecules from the solvent cage was observed. PMID:23443649

  14. Intramolecular energy- and electron-transfer reactions in polymetallic complexes. Annual report

    SciTech Connect

    Peterson, J.D.

    1991-12-01

    The complexes (tpy)Ru(II)(tpp)Co(III)(PPhEt{sub 2})H{sub 2}{sup 3+}, (NC){sub 3}Fe(II)(tpp)Co(III)(PPhEt{sub 2})H{sub 2} and (NC){sub 3}Fe(II)(tpp)Co(III)(PPh{sub 3})H{sub 2} (where tpp = 2,3,5,6-tetrakis(2{prime}-pyridyl)pyrazine), were prepared and their photochemistry studied. Reasons for the low quantum yields for H{sub 2} production are discussed briefly. A series of FeRuRh complexes is being prepared. Plans for the coming year on intramolecular energy transfer and charge separation are discussed.

  15. A resonance mechanism of efficient energy transfer mediated by Fenna-Matthews-Olson complex

    NASA Astrophysics Data System (ADS)

    Alicki, Robert; Miklaszewski, Wiesław

    2012-04-01

    The Wigner-Weisskopf-type model developed by Alicki and Giraldi [J. Phys. B 44, 154020 (2011)], 10.1088/0953-4075/44/15/154020 is applied to the biological process of energy transfer from a large peripheral light harvesting antenna to the reaction center. This process is mediated by the Fenna-Matthews-Olson (FMO) photosynthetic complex with a remarkably high efficiency. The proposed model provides a simple resonance mechanism of this phenomenon employing exciton coherent motion and is described by analytical formulas. A coupling to the vibrational environment is a necessary component of this mechanism as well as a fine-tuning of the FMO complex Hamiltonian. The role of the relatively strong coupling to the energy sink in achieving the resonance condition and the absence of heating of the vibrational environment are emphasized.

  16. 77 FR 21579 - Agency Information Collection Activities: Transfer of Cargo to a Container Station

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-04-10

    ...U.S. Customs and Border Protection (CBP) of the Department of Homeland Security will be submitting the following information collection request to the Office of Management and Budget (OMB) for review and approval in accordance with the Paperwork Reduction Act: Transfer of Cargo to a Container Station. This is a proposed extension of an information collection that was previously approved. CBP......

  17. Administrative Aspects of Third World Library Development: The Five "Pillars" of Sustainable Information Transfer.

    ERIC Educational Resources Information Center

    Emerson, Susan Vince; And Others

    Third World libraries, as a rule, receive information technology, technical assistance, and training as part of international development projects. Library improvements and their intended objective, information transfer, are more effective and lasting if key administrative and policy issues are addressed by the projects. Critical success factors…

  18. Invited Reaction: Informal Learning and the Transfer of Learning--How Managers Develop Proficiency

    ERIC Educational Resources Information Center

    Marsick, Victoria J.

    2003-01-01

    Enos, Kehrhahn, and Bell have made an important contribution to measuring informal learning and its transfer as proficiency in a set of company-identified managerial skills. Measurement of informal learning is at the crux of research that seeks to link learning outcomes to other indicators of effective performance. The ability to show how informal…

  19. 78 FR 59772 - Proposed Information Collection (Evidence for Transfer of Entitlement of Education Benefits...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2013-09-27

    ... through Federal Docket Management System (FDMS) at www.Regulations.gov or to Nancy J. Kessinger, Veterans... the Office of Management and Budget (OMB) for each collection of information they conduct or sponsor... AFFAIRS Proposed Information Collection (Evidence for Transfer of Entitlement of Education...

  20. 75 FR 68035 - Proposed Information Collection (Evidence for Transfer of Entitlement of Education Benefits...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-11-04

    ... through Federal Docket Management System (FDMS) at http://www.Regulations.gov or to Nancy J. Kessinger... the Office of Management and Budget (OMB) for each collection of information they conduct or sponsor... AFFAIRS Proposed Information Collection (Evidence for Transfer of Entitlement of Education...

  1. Synthesis and characterization of highly conductive charge-transfer complexes using positron annihilation spectroscopy.

    PubMed

    Adam, Abdel Majid A; Refat, Moamen S; Sharshar, T; Heiba, Z K

    2012-09-01

    Molecular charge-transfer complexes of the tetramethylethylenediamine (TMEDA) with picric acid (Pi-OH), benzene-1,4-diol (QL), tin(IV) tetrachloride (SnCl(4)), iodine, bromine, and zinc chloride (ZnCl(2)) have been synthesized and investigated by elemental and thermal analysis, electronic, infrared, Raman and proton-NMR, energy-dispersive X-ray spectroscopy, X-ray powder diffraction and positron annihilation lifetime spectroscopy, and scanning electron microscopy. In this work, three types of acceptors π-acceptors (Pi-OH and QL), σ-acceptors (iodine and bromine), and vacant orbital acceptors (SnCl(4) and ZnCl(2)) were covered. The results of elemental analysis indicated that the CT complexes were formed with ratios 1:1 and 1:2 for QL, SnCl(4), and ZnCl(2) acceptors and iodine, Pi-OH, and Br(2) acceptors, respectively. The type of chelating between the TMEDA donor and the mentioned acceptors depends upon the behavior of both items. The positron annihilation lifetime parameters were found to be dependent on the structure, electronic configuration, and the power of acceptors. The correlation between these parameters and the molecular weight and biological activities of studied complexes was also observed. Regarding the electrical properties, the AC conductivity and the dielectric coefficients were measured as a function of frequency at room temperature. The TMEDA charge-transfer complexes were screened against antibacterial (Escherichia coli, Staphylococcus aureus, Bacillus subtilis, and Pseudomonas aeruginosa) and antifungal (Aspergillus flavus and Candida albicans) activities. PMID:22595252

  2. Determining Protein Complex Structures Based on a Bayesian Model of in Vivo Förster Resonance Energy Transfer (FRET) Data*

    PubMed Central

    Bonomi, Massimiliano; Pellarin, Riccardo; Kim, Seung Joong; Russel, Daniel; Sundin, Bryan A.; Riffle, Michael; Jaschob, Daniel; Ramsden, Richard; Davis, Trisha N.; Muller, Eric G. D.; Sali, Andrej

    2014-01-01

    The use of in vivo Förster resonance energy transfer (FRET) data to determine the molecular architecture of a protein complex in living cells is challenging due to data sparseness, sample heterogeneity, signal contributions from multiple donors and acceptors, unequal fluorophore brightness, photobleaching, flexibility of the linker connecting the fluorophore to the tagged protein, and spectral cross-talk. We addressed these challenges by using a Bayesian approach that produces the posterior probability of a model, given the input data. The posterior probability is defined as a function of the dependence of our FRET metric FRETR on a structure (forward model), a model of noise in the data, as well as prior information about the structure, relative populations of distinct states in the sample, forward model parameters, and data noise. The forward model was validated against kinetic Monte Carlo simulations and in vivo experimental data collected on nine systems of known structure. In addition, our Bayesian approach was validated by a benchmark of 16 protein complexes of known structure. Given the structures of each subunit of the complexes, models were computed from synthetic FRETR data with a distance root-mean-squared deviation error of 14 to 17 Å. The approach is implemented in the open-source Integrative Modeling Platform, allowing us to determine macromolecular structures through a combination of in vivo FRETR data and data from other sources, such as electron microscopy and chemical cross-linking. PMID:25139910

  3. Hidden Behavior Prediction of Complex Systems Based on Hybrid Information.

    PubMed

    Zhou, Zhi-Jie; Hu, Chang-Hua; Zhang, Bang-Cheng; Xu, Dong-Ling; Chen, Yu-Wang

    2013-04-01

    It is important to predict both observable and hidden behaviors in complex engineering systems. However, compared with observable behavior, it is often difficult to establish a forecasting model for hidden behavior. The existing methods for predicting the hidden behavior cannot effectively and simultaneously use the hybrid information with uncertainties that include qualitative knowledge and quantitative data. Although belief rule base (BRB) has been employed to predict the observable behavior using the hybrid information with uncertainties, it is still not applicable to predict the hidden behavior directly. As such, in this paper, a new BRB-based model is proposed to predict the hidden behavior. In the proposed BRB-based model, the initial values of parameters are usually given by experts, thus some of them may not be accurate, which can lead to inaccurate prediction results. In order to solve the problem, a parameter estimation algorithm for training the parameters of the forecasting model is further proposed on the basis of maximum likelihood algorithm. Using the hybrid information with uncertainties, the proposed model can combine together with the parameter estimation algorithm and improve the forecasting precision in an integrated and effective manner. A case study is conducted to demonstrate the capability and potential applications of the proposed forecasting model with the parameter estimation algorithm. PMID:22907969

  4. Electron transfer in the P450cam/PDX complex. The QM/MM e-pathway.

    PubMed

    Wallrapp, Frank; Masone, Diego; Guallar, Victor

    2008-12-18

    Electron transfer processes are simple but crucial reactions in biochemistry, being one of the main steps in almost all enzymatic cycles. Obtaining an atomic description of the transfer pathway is a difficult task, at both the experimental and theoretical levels. Here we combine protein-protein docking algorithms, protein structure prediction methodologies and mixed quantum mechanics/molecular mechanics techniques to map the electron transfer pathway between cytochrome P450 camphor and its redox partner, putidaredoxin. Although the mechanism of interaction and electron transfer for this redox couple has been under investigation for over 30 years, the exact mechanism and electron transfer pathway has not been fully understood, yet. Our results report the first ab initio quantum chemistry description of the electron migration. The obtained electron transfer pathway indicates the key role of Arg112 of P450 and Asp38 of PDX and the existence of slightly different electron transfer pathways for different protein-protein complexes. PMID:18823106

  5. Information transfer dynamics in fixed-pathways networks

    NASA Astrophysics Data System (ADS)

    Moyano, Luis G.; Cárdenas, Juan P.; Salcedo, Jorge; Mouronte, Mary Luz; Benito, Rosa M.

    2011-03-01

    Most complex technological networks are defined in such a way that their global properties are manifested at a dynamical level. An example of this is when internal dynamical processes are constrained to predefined pathways, without the possibility of alternate routes. For instance, large corporation software networks, where several flow processes take place, are typically routed along specific paths. In this work, we propose a model to describe the global characteristics of this kind of processes, where the dynamics depends on the state of the nodes, represented by two possibilities: responsive or blocked. We present numerical simulations that show rich global behavior with unexpected emerging properties. In particular, we show that two different regimes appear as a function of the total network load. Each regime is characterized by developing either a unimodal or a bimodal distribution for the density of responsive nodes, directly related to global efficiency. We provide a detailed explanation for the main characteristics of our results as well as an analysis of the implications for real technological systems.

  6. Information transfer dynamics in fixed-pathways networks.

    PubMed

    Moyano, Luis G; Cárdenas, Juan P; Salcedo, Jorge; Mouronte, Mary Luz; Benito, Rosa M

    2011-03-01

    Most complex technological networks are defined in such a way that their global properties are manifested at a dynamical level. An example of this is when internal dynamical processes are constrained to predefined pathways, without the possibility of alternate routes. For instance, large corporation software networks, where several flow processes take place, are typically routed along specific paths. In this work, we propose a model to describe the global characteristics of this kind of processes, where the dynamics depends on the state of the nodes, represented by two possibilities: responsive or blocked. We present numerical simulations that show rich global behavior with unexpected emerging properties. In particular, we show that two different regimes appear as a function of the total network load. Each regime is characterized by developing either a unimodal or a bimodal distribution for the density of responsive nodes, directly related to global efficiency. We provide a detailed explanation for the main characteristics of our results as well as an analysis of the implications for real technological systems. PMID:21456840

  7. Morphology-induced information transfer in bat sonar.

    PubMed

    Reijniers, Jonas; Vanderelst, Dieter; Peremans, Herbert

    2010-10-01

    It has been argued that an important part of understanding bat echolocation comes down to understanding the morphology of the bat sound processing apparatus. In this Letter we present a method based on information theory that allows us to assess target localization performance of bat sonar, without a priori knowledge on the position, size, or shape of the reflecting target. We demonstrate this method using simulated directivity patterns of the frequency-modulated bat Micronycteris microtis. The results of this analysis indicate that the morphology of this bat's sound processing apparatus has evolved to be a compromise between sensitivity and accuracy with the pinnae and the noseleaf playing different roles. PMID:21230873

  8. Efficient transfer of weather information to the pilot in flight

    NASA Technical Reports Server (NTRS)

    Mcfarland, R. H.

    1982-01-01

    Efficient methods for providing weather information to the pilot in flight are summarized. Use of discrete communications channels in the aeronautical, VHF band or subcarriers in the VOR navigation band are considered the best possibilities. Data rates can be provided such that inputs to the ground based transmitters from 2400 band telephone lines are easily accommodated together with additional data. The crucial weather data considered for uplinking are identified as radar reflectivity patterns relating to precipitation, spherics data, hourly sequences, nowcasts, forecasts, cloud top heights with freezing and icing conditions, the critical weather map and satellite maps. NEXRAD, the ground based, Doppler weather radar which will produce an improved weather product also encourages use of an uplink to fully utilize its capability to improve air safety.

  9. Variation of geometries and electron properties along proton transfer in strong hydrogen-bond complexes

    NASA Astrophysics Data System (ADS)

    Pacios, L. F.; Gálvez, O.; Gómez, P. C.

    2005-06-01

    Proton transfer in hydrogen-bond systems formed by 4-methylimidazole in both neutral and protonated cationic forms and by acetate anion are studied by means of MP2/6-311++G(d,p) ab initio calculations. These two complexes model the histidine (neutral and protonated)-aspartate diad present in the active sites of enzymes the catalytic mechanism of which involves the formation of strong hydrogen bonds. We investigate the evolution of geometries, natural bond orbital populations of bonds and electron lone pairs, topological descriptors of the electron density, and spatial distributions of the electron localization function along the process N-H ⋯O→N⋯H⋯O→N⋯H-O, which represents the stages of the H-transfer. Except for a sudden change in the population of electron lone pairs in N and O at the middle N...H...O stage, all the properties analyzed show a smooth continuous behavior along the covalent → hydrogen bond transit inherent to the transfer, without any discontinuity that could identify a formation or breaking of the hydrogen bond. This way, the distinction between covalent or hydrogen-bonding features is associated to subtle electron rearrangement at the intermolecular space.

  10. Charge-transfer complexes and their role in exciplex emission and near-infrared photovoltaics.

    PubMed

    Ng, Tsz-Wai; Lo, Ming-Fai; Fung, Man-Keung; Zhang, Wen-Jun; Lee, Chun-Sing

    2014-08-20

    Charge transfer and interactions at organic heterojunctions (OHJs) are known to have critical influences on various properties of organic electronic devices. In this Research News article, a short review is given from the electronic viewpoint on how the local molecular interactions and interfacial energetics at P/N OHJs contribute to the recombination/dissociation of electron-hole pairs. Very often, the P-type materials donate electrons to the N-type materials, giving rise to charge-transfer complexes (CTCs) with a P(δ+) -N(δ-) configuration. A recently observed opposite charge-transfer direction in OHJs is also discussed (i.e., N-type material donates electrons to P-type material to form P(δ-) -N(δ+) ). Recent studies on the electronic structures of CTC-forming material pairs are also summarized. The formation of P(δ-) -N(δ+) -type CTCs and their correlations with exciplex emission are examined. Furthermore, the potential applications of CTCs in NIR photovoltaic devices are reviewed. PMID:24799189

  11. A general theoretical model for electron transfer reactions in complex systems.

    PubMed

    Amadei, Andrea; Daidone, Isabella; Aschi, Massimiliano

    2012-01-28

    In this paper we present a general theoretical-computational model for treating electron transfer reactions in complex atomic-molecular systems. The underlying idea of the approach, based on unbiased first-principles calculations at the atomistic level, utilizes the definition and the construction of the Diabatic Perturbed states of the involved reactive partners (i.e. the quantum centres in our perturbation approach) as provided by the interaction with their environment, including their mutual interaction. In this way we reconstruct the true Adiabatic states of the reactive partners characterizing the electron transfer process as the fluctuation of the electronic density due to the fluctuating perturbation. Results obtained by using a combination of Molecular Dynamics simulation and the Perturbed Matrix Method on a prototypical intramolecular electron transfer (from 2-(9,9'-dimethyl)fluorene to the 2-naphthalene group separated by a steroidal 5-α-androstane skeleton) well illustrate the accuracy of the method in reproducing both the thermodynamics and the kinetics of the process. PMID:22158942

  12. Charge transfer of iron(III) monomeric and oligomeric aqua hydroxo complexes: semiempirical investigation into photoactivity.

    PubMed

    Lopes, Ludovic; de Laat, Joseph; Legube, Bernard

    2002-05-01

    Aqueous hydrolyses of iron(III) solutions were studied using electronic spectroscopy. Complete spectra from 200 to 800 nm were obtained for the four ferric aqua hydroxo complexes: Fe(H(2)O)(6)(3+), Fe(OH)(H(2)O)(5)(2+), Fe(OH)(2)(H(2)O)(4)(+), and the dimer Fe(2)(mu-Omicron Eta)(2)(H(2)O)(8)(4+). Semiempirical Zindo/s calculations were employed to assign which types of electronic transfers are involved so that the photoactivity as regards the photoreduction dissociation Fe(III)(aq) Fe(II)(aq) + OH* can be discussed. Fe(3+) exhibits two LMCT from non-bonding p orbitals (nLp) located at 190 and 240 nm. Fe(OH)(2+) shows two major nLp(OH) --> d transitions at 205 and 295 nm. As regards its geometry, computed investigations using an Fe-OH distance of 2.05 A better fit than using a shorter distance ( approximately 1.8 A); the same conclusion remains constant for all hydroxo complexes. The dihydroxo form's spectrum was confronted to its common cis and trans expectable isomers plus an unusual pentacoordinate one. Even if the trans isomer is supposed to be the lowest Gibbs free energy species in solution, there is some evidence of the presence of the cis form; hence, both species must be close in energy. Other isolated nLp(OH) --> d transfer wavelengths are 235, 245, and 335 nm. As for the dimer, this study provides some clue in favor of the bis(mu-hydroxo)) description. Both water and hydroxo ligands are involved along the electronic transitions toward only d(1) metal-centered orbitals at 220 and 260 nm for H(2)O, 335 and 470 nm for OH(-), and 205 nm for both. Charge transfers for the hydrogen oxide bridge form Fe(2)(mu-Eta(3)Omicron(2))(H(2)O)(8)(5+) were also computed. Finally predictions about the two bis(mu-hydroxo) bridge trimer Fe(3)(OH)(4)(H(2)O)(10)(5+) enable one to foresee a huge and broad charge transfer in the UV region (approximately 240 nm) followed by a multi nLp(OH) --> d(1) transfer extending up to approximately 650 nm. PMID:11978119

  13. Chemical mechanism of surface-enhanced Raman scattering via charge transfer in fluorenone-Ag complex.

    PubMed

    Wang, Jing; Li, Yafei; Wu, Shiwei; Song, Peng; Xia, Lixin

    2016-06-01

    The intermolecular interaction between fluorenone (FN) and silver surfaces was investigated experimentally and theoretically. The structural, electronic and optical properties of the FN-Ag complex indicate that the carbonyl group O atom in FN molecules is the adsorbed position site to attach the silver substrate through the weak bond O…Ag. The analysis of vibrational modes and Raman activity of the largely enhanced Raman peaks using two FN-Ag4-x (x  =  l, s) complex models reveals that only the a1 vibrational modes with C 2v symmetry are selectively enhanced, from the point view of the change of dipole moment and polarizability induced by the interaction between FN and Ag4 substrate. Furthermore, the direct visualized evidence of the surface-enhanced Raman scattering (SERS) chemical enhancement mechanism for the FN-Ag complex is presented. The results reveal that only the intermolecular charge transfer with π-π transition characterization between FN and an Ag4 cluster facilitates the resonance Raman process and is directly responsible for chemical enhancement of Raman scattering of the FN-Ag complex. PMID:27147706

  14. Chemical mechanism of surface-enhanced Raman scattering via charge transfer in fluorenone–Ag complex

    NASA Astrophysics Data System (ADS)

    Wang, Jing; Li, Yafei; Wu, Shiwei; Song, Peng; Xia, Lixin

    2016-06-01

    The intermolecular interaction between fluorenone (FN) and silver surfaces was investigated experimentally and theoretically. The structural, electronic and optical properties of the FN–Ag complex indicate that the carbonyl group O atom in FN molecules is the adsorbed position site to attach the silver substrate through the weak bond O…Ag. The analysis of vibrational modes and Raman activity of the largely enhanced Raman peaks using two FN–Ag4-x (x  =  l, s) complex models reveals that only the a1 vibrational modes with C 2v symmetry are selectively enhanced, from the point view of the change of dipole moment and polarizability induced by the interaction between FN and Ag4 substrate. Furthermore, the direct visualized evidence of the surface-enhanced Raman scattering (SERS) chemical enhancement mechanism for the FN–Ag complex is presented. The results reveal that only the intermolecular charge transfer with π–π transition characterization between FN and an Ag4 cluster facilitates the resonance Raman process and is directly responsible for chemical enhancement of Raman scattering of the FN–Ag complex.

  15. Spectrophotometric and electrical studies of charge-transfer complexes of sodium flucloxacillin with π-acceptors

    NASA Astrophysics Data System (ADS)

    Refat, Moamen S.; El-Didamony, Akram M.

    2006-11-01

    The present study is interested to develop a simple, rapid and accurate spectrophotometric method for determination of sodium flucloxacillin (fluc) in pure form and pharmaceutical formulations. The charge-transfer (CT) interactions between sodium flucloxacillin as electron donor and chloranilic acid (CLA), dichloroquinone 4-chloroimide (DCQ), 2,3-dichloro-5,6-dicyano- p-benzoquinone (DDQ) and 7,7,8,8 tetracyano- p-quinodimethane (TCNQ), as π-electron acceptors have been investigated spectrophotometrically. Different variables affecting the reaction were studied and optimized. Under the optimum conditions, linear relationships with good correlation coefficients (0.9979-0.9995) were found between the absorbance and the concentration of the drug in the range 16-880 μg ml -1. The proposed methods were applied successfully to the determination of the examined drug either in pure or pharmaceutical dosage forms with good accuracy and precision. The formation of the CT-complexes and the sites of interaction were confirmed by elemental analysis CHN, UV-vis, IR, 1H NMR and mass spectra techniques. Based on Job's method of continuous variation plots, the obtained results indicate the formation of 1:1 charge-transfer complexes with the general formula [(fluc)(acceptor)]. Statistical analysis of the obtained results showed no significant difference between the proposed method and official method.

  16. Quinone-dependent proton transfer pathways in the photosynthetic cytochrome b6f complex.

    PubMed

    Hasan, S Saif; Yamashita, Eiki; Baniulis, Danas; Cramer, William A

    2013-03-12

    As much as two-thirds of the proton gradient used for transmembrane free energy storage in oxygenic photosynthesis is generated by the cytochrome b6f complex. The proton uptake pathway from the electrochemically negative (n) aqueous phase to the n-side quinone binding site of the complex, and a probable route for proton exit to the positive phase resulting from quinol oxidation, are defined in a 2.70-Å crystal structure and in structures with quinone analog inhibitors at 3.07 Å (tridecyl-stigmatellin) and 3.25-Å (2-nonyl-4-hydroxyquinoline N-oxide) resolution. The simplest n-side proton pathway extends from the aqueous phase via Asp20 and Arg207 (cytochrome b6 subunit) to quinone bound axially to heme c(n). On the positive side, the heme-proximal Glu78 (subunit IV), which accepts protons from plastosemiquinone, defines a route for H(+) transfer to the aqueous phase. These pathways provide a structure-based description of the quinone-mediated proton transfer responsible for generation of the transmembrane electrochemical potential gradient in oxygenic photosynthesis. PMID:23440205

  17. Spectrophotometric and electrical studies of charge-transfer complexes of sodium flucloxacillin with pi-acceptors.

    PubMed

    Refat, Moamen S; El-Didamony, Akram M

    2006-11-01

    The present study is interested to develop a simple, rapid and accurate spectrophotometric method for determination of sodium flucloxacillin (fluc) in pure form and pharmaceutical formulations. The charge-transfer (CT) interactions between sodium flucloxacillin as electron donor and chloranilic acid (CLA), dichloroquinone 4-chloroimide (DCQ), 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ) and 7,7,8,8 tetracyano-p-quinodimethane (TCNQ), as pi-electron acceptors have been investigated spectrophotometrically. Different variables affecting the reaction were studied and optimized. Under the optimum conditions, linear relationships with good correlation coefficients (0.9979-0.9995) were found between the absorbance and the concentration of the drug in the range 16-880 microg ml(-1). The proposed methods were applied successfully to the determination of the examined drug either in pure or pharmaceutical dosage forms with good accuracy and precision. The formation of the CT-complexes and the sites of interaction were confirmed by elemental analysis CHN, UV-vis, IR, (1)H NMR and mass spectra techniques. Based on Job's method of continuous variation plots, the obtained results indicate the formation of 1:1 charge-transfer complexes with the general formula [(fluc)(acceptor)]. Statistical analysis of the obtained results showed no significant difference between the proposed method and official method. PMID:16527531

  18. Excitation energy transfer between Light-harvesting complex II and Photosystem I in reconstituted membranes.

    PubMed

    Akhtar, Parveen; Lingvay, Mónika; Kiss, Teréz; Deák, Róbert; Bóta, Attila; Ughy, Bettina; Garab, Győző; Lambrev, Petar H

    2016-04-01

    Light-harvesting complex II (LHCII), the major peripheral antenna of Photosystem II in plants, participates in several concerted mechanisms for regulation of the excitation energy and electron fluxes in thylakoid membranes. In part, these include interaction of LHCII with Photosystem I (PSI) enhancing the latter's absorption cross-section - for example in the well-known state 1 - state 2 transitions or as a long-term acclimation to high light. In this work we examined the capability of LHCII to deliver excitations to PSI in reconstituted membranes in vitro. Proteoliposomes with native plant thylakoid membrane lipids and different stoichiometric ratios of LHCII:PSI were reconstituted and studied by steady-state and time-resolved fluorescence spectroscopy. Fluorescence emission from LHCII was strongly decreased in PSI-LHCII membranes due to trapping of excitations by PSI. Kinetic modelling of the time-resolved fluorescence data revealed the existence of separate pools of LHCII distinguished by the time scale of energy transfer. A strongly coupled pool, equivalent to one LHCII trimer per PSI, transferred excitations to PSI with near-unity efficiency on a time scale of less than 10ps but extra LHCIIs also contributed significantly to the effective antenna size of PSI, which could be increased by up to 47% in membranes containing 3 LHCII trimers per PSI. The results demonstrate a remarkable competence of LHCII to increase the absorption cross-section of PSI, given the opportunity that the two types of complexes interact in the membrane. PMID:26827938

  19. Transferring an optimized TAP-toolbox for the isolation of protein complexes to a portfolio of rice tissues.

    PubMed

    Dedecker, Maarten; Van Leene, Jelle; De Winne, Nancy; Eeckhout, Dominique; Persiau, Geert; Van De Slijke, Eveline; Cannoot, Bernard; Vercruysse, Leen; Dumoulin, Lies; Wojsznis, Nathalie; Gevaert, Kris; Vandenabeele, Steven; De Jaeger, Geert

    2016-06-01

    Proteins are the cell's functional entities. Rather than operating independently, they interact with other proteins. Capturing in vivo protein complexes is therefore crucial to gain understanding of the function of a protein in a cellular context. Affinity purification coupled to mass spectrometry has proven to yield a wealth of information about protein complex constitutions for a broad range of organisms. For Oryza sativa, the technique has been initiated in callus and shoots, but has not been optimized ever since. We translated an optimized tandem affinity purification (TAP) approach from Arabidopsis thaliana toward Oryza sativa, and demonstrate its applicability in a variety of rice tissues. A list of non-specific and false positive interactors is presented, based on re-occurrence over more than 170 independent experiments, to filter bona fide interactors. We demonstrate the sensitivity of our approach by isolating the complexes for the rice ANAPHASE PROMOTING COMPLEX SUBUNIT 10 (APC10) and CYCLIN-DEPENDENT KINASE D (CDKD) proteins from the proliferation zone of the emerging fourth leaf. Next to APC10 and CDKD, we tested several additional baits in the different rice tissues and reproducibly retrieved at least one interactor for 81.4 % of the baits screened for in callus tissue and T1 seedlings. By transferring an optimized TAP tag combined with state-of-the-art mass spectrometry, our TAP protocol enables the discovery of interactors for low abundance proteins in rice and opens the possibility to capture complex dynamics by comparing tissues at different stages of a developing rice organ. PMID:27003905

  20. Analytical studies on the charge transfer complexes of loperamide hydrochloride and trimebutine drugs. Spectroscopic and thermal characterization of CT complexes

    NASA Astrophysics Data System (ADS)

    Elqudaby, Hoda M.; Mohamed, Gehad G.; El-Din, Ghada M. G.

    2014-08-01

    Charge transfer complexes of loperamide hydrochloride (LOP.HCl) and trimebutine (TB) drugs as electron donor with 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ), tetracyanoethylene (TCNE) and 7,7,8,8-tetracyanoquinodimethane (TCNQ) as π-acceptors in acetonitrile were investigated spectrophotometrically to determine the cited drugs in pure and dosage forms. The reaction gives highly coloured complex species which are measured spectrophotometrically at 460, 415 and 842 nm in case of LOP.HCl and at 455, 414 and 842 nm in case of TB using DDQ, TCNE and TCNQ reagents, respectively. The optimum experimental conditions have been studied carefully and optimized. Beer’s law was obeyed over the concentration ranges of 47.70-381.6, 21.50-150.5 and 10.00-100.0 μg mL-1 for LOP.HCl and 37.85-264.9, 38.75-310.0 and 7.75-155.0 μg mL-1 for TB using DDQ, TCNE and TCNQ reagents, respectively. Sandell sensitivity, standard deviation, relative standard deviation, limit of detection and quantification were calculated. The obtained data refer to high accuracy and precision of the proposed method. These results are also confirmed by inter and intra-day precision with percent recovery of 99.18-101.1% and 99.32-101.4% in case of LOP.HCl and 98.00-102.0% and 97.50-101.4% in case of TB using DDQ, TCNE and TCNQ reagents for intra- and inter-day, respectively. These data were compared with those obtained using official methods for the determination of the cited drugs. The stability constants of the CT complexes were determined. The final products of the reaction were isolated and characterized using FT-IR, 1H NMR, elemental analysis and thermogravimetric analysis (TG). The stoichiometry and apparent formation constant of the complexes formed were determined by applying the conventional spectrophotometric molar ratio method.

  1. A novel information transferring approach for the classification of remote sensing images

    NASA Astrophysics Data System (ADS)

    Gao, Jianqiang; Xu, Lizhong; Shen, Jie; Huang, Fengchen; Xu, Feng

    2015-12-01

    Traditional remote sensing images classification methods focused on using a large amount of labeled target data to train an efficient classification model. However, these approaches were generally based on the target data without considering a host of auxiliary data or the additional information of auxiliary data. If the valuable information from auxiliary data could be successfully transferred to the target data, the performance of the classification model would be improved. In addition, from the perspective of practical application, these valuable information from auxiliary data should be fully used. Therefore, in this paper, based on the transfer learning idea, we proposed a novel information transferring approach to improve the remote sensing images classification performance. The main rationale of this approach is that first, the information of the same areas associated with each pixel is modeled as the intra-class set, and the information of different areas associated with each pixel is modeled as the inter-class set, and then the obtained texture feature information of each area from auxiliary is transferred to the target data set such that the inter-class set is separated and intra-class set is gathered as far as possible. Experiments show that the proposed approach is effective and feasible.

  2. A tool for filtering information in complex systems

    NASA Astrophysics Data System (ADS)

    Tumminello, M.; Aste, T.; Di Matteo, T.; Mantegna, R. N.

    2005-07-01

    We introduce a technique to filter out complex data sets by extracting a subgraph of representative links. Such a filtering can be tuned up to any desired level by controlling the genus of the resulting graph. We show that this technique is especially suitable for correlation-based graphs, giving filtered graphs that preserve the hierarchical organization of the minimum spanning tree but containing a larger amount of information in their internal structure. In particular in the case of planar filtered graphs (genus equal to 0), triangular loops and four-element cliques are formed. The application of this filtering procedure to 100 stocks in the U.S. equity markets shows that such loops and cliques have important and significant relationships with the market structure and properties. This paper was submitted directly (Track II) to the PNAS office.Abbreviations: MST, minimum spanning tree; PMFG, Planar Maximally Filtered Graph; r-clique, clique of r elements.

  3. A tool for filtering information in complex systems.

    PubMed

    Tumminello, M; Aste, T; Di Matteo, T; Mantegna, R N

    2005-07-26

    We introduce a technique to filter out complex data sets by extracting a subgraph of representative links. Such a filtering can be tuned up to any desired level by controlling the genus of the resulting graph. We show that this technique is especially suitable for correlation-based graphs, giving filtered graphs that preserve the hierarchical organization of the minimum spanning tree but containing a larger amount of information in their internal structure. In particular in the case of planar filtered graphs (genus equal to 0), triangular loops and four-element cliques are formed. The application of this filtering procedure to 100 stocks in the U.S. equity markets shows that such loops and cliques have important and significant relationships with the market structure and properties. PMID:16027373

  4. Enabling complex queries to drug information sources through functional composition.

    PubMed

    Peters, Lee; Mortensen, Jonathan; Nguyen, Thang; Bodenreider, Olivier

    2013-01-01

    Our objective was to enable an end-user to create complex queries to drug information sources through functional composition, by creating sequences of functions from application program interfaces (API) to drug terminologies. The development of a functional composition model seeks to link functions from two distinct APIs. An ontology was developed using Protégé to model the functions of the RxNorm and NDF-RT APIs by describing the semantics of their input and output. A set of rules were developed to define the interoperable conditions for functional composition. The operational definition of interoperability between function pairs is established by executing the rules on the ontology. We illustrate that the functional composition model supports common use cases, including checking interactions for RxNorm drugs and deploying allergy lists defined in reference to drug properties in NDF-RT. This model supports the RxMix application (http://mor.nlm.nih.gov/RxMix/), an application we developed for enabling complex queries to the RxNorm and NDF-RT APIs. PMID:23920645

  5. Information-driven modeling of protein-peptide complexes.

    PubMed

    Trellet, Mikael; Melquiond, Adrien S J; Bonvin, Alexandre M J J

    2015-01-01

    Despite their biological importance in many regulatory processes, protein-peptide recognition mechanisms are difficult to study experimentally at the structural level because of the inherent flexibility of peptides and the often transient interactions on which they rely. Complementary methods like biomolecular docking are therefore required. The prediction of the three-dimensional structure of protein-peptide complexes raises unique challenges for computational algorithms, as exemplified by the recent introduction of protein-peptide targets in the blind international experiment CAPRI (Critical Assessment of PRedicted Interactions). Conventional protein-protein docking approaches are often struggling with the high flexibility of peptides whose short sizes impede protocols and scoring functions developed for larger interfaces. On the other side, protein-small ligand docking methods are unable to cope with the larger number of degrees of freedom in peptides compared to small molecules and the typically reduced available information to define the binding site. In this chapter, we describe a protocol to model protein-peptide complexes using the HADDOCK web server, working through a test case to illustrate every steps. The flexibility challenge that peptides represent is dealt with by combining elements of conformational selection and induced fit molecular recognition theories. PMID:25555727

  6. Enabling Complex Queries to Drug Information Sources through Functional Composition

    PubMed Central

    Peters, Lee; Mortensen, Jonathan; Nguyen, Thang; Bodenreider, Olivier

    2015-01-01

    Our objective was to enable an end-user to create complex queries to drug information sources through functional composition, by creating sequences of functions from application program interfaces (API) to drug terminologies. The development of a functional composition model seeks to link functions from two distinct APIs. An ontology was developed using Protégé to model the functions of the RxNorm and NDF-RT APIs by describing the semantics of their input and output. A set of rules were developed to define the interoperable conditions for functional composition. The operational definition of interoperability between function pairs is established by executing the rules on the ontology. We illustrate that the functional composition model supports common use cases, including checking interactions for RxNorm drugs and deploying allergy lists defined in reference to drug properties in NDF-RT. This model supports the RxMix application (http://mor.nlm.nih.gov/RxMix/), an application we developed for enabling complex queries to the RxNorm and NDF-RT APIs. PMID:23920645

  7. Information Transfer in Gonadotropin-releasing Hormone (GnRH) Signaling

    PubMed Central

    Garner, Kathryn L.; Perrett, Rebecca M.; Voliotis, Margaritis; Bowsher, Clive; Pope, George R.; Pham, Thanh; Caunt, Christopher J.; Tsaneva-Atanasova, Krasimira; McArdle, Craig A.

    2016-01-01

    Cell signaling pathways are noisy communication channels, and statistical measures derived from information theory can be used to quantify the information they transfer. Here we use single cell signaling measures to calculate mutual information as a measure of information transfer via gonadotropin-releasing hormone (GnRH) receptors (GnRHR) to extracellular signal-regulated kinase (ERK) or nuclear factor of activated T-cells (NFAT). This revealed mutual information values <1 bit, implying that individual GnRH-responsive cells cannot unambiguously differentiate even two equally probable input concentrations. Addressing possible mechanisms for mitigation of information loss, we focused on the ERK pathway and developed a stochastic activation model incorporating negative feedback and constitutive activity. Model simulations revealed interplay between fast (min) and slow (min-h) negative feedback loops with maximal information transfer at intermediate feedback levels. Consistent with this, experiments revealed that reducing negative feedback (by expressing catalytically inactive ERK2) and increasing negative feedback (by Egr1-driven expression of dual-specificity phosphatase 5 (DUSP5)) both reduced information transfer from GnRHR to ERK. It was also reduced by blocking protein synthesis (to prevent GnRH from increasing DUSP expression) but did not differ for different GnRHRs that do or do not undergo rapid homologous desensitization. Thus, the first statistical measures of information transfer via these receptors reveals that individual cells are unreliable sensors of GnRH concentration and that this reliability is maximal at intermediate levels of ERK-mediated negative feedback but is not influenced by receptor desensitization. PMID:26644469

  8. Electron-Transfer Pathways in the Heme and Quinone-Binding Domain of Complex II (Succinate Dehydrogenase)

    PubMed Central

    2015-01-01

    Single electron transfers have been examined in complex II (succinate:ubiquinone oxidoreductase) by the method of pulse radiolysis. Electrons are introduced into the enzyme initially at the [3Fe–4S] and ubiquinone sites followed by intramolecular equilibration with the b heme of the enzyme. To define thermodynamic and other controlling parameters for the pathways of electron transfer in complex II, site-directed variants were constructed and analyzed. Variants at SdhB-His207 and SdhB-Ile209 exhibit significantly perturbed electron transfer between the [3Fe–4S] cluster and ubiquinone. Analysis of the data using Marcus theory shows that the electronic coupling constants for wild-type and variant enzyme are all small, indicating that electron transfer occurs by diabatic tunneling. The presence of the ubiquinone is necessary for efficient electron transfer to the heme, which only slowly equilibrates with the [3Fe–4S] cluster in the absence of the quinone. PMID:24559074

  9. Information management, today and tomorrow. [acquisition, manipulation, transfer, and display of information

    NASA Technical Reports Server (NTRS)

    Pryor, H. E.

    1975-01-01

    Current problems and future trends in information management are briefly summarized in relation to scientific and technical information management systems and management of management information (planning, marketing, and operations).

  10. Hydration effect on proton transfer in melamine-cyanuric acid complex.

    PubMed

    Yan, Shihai; Kang, Baotao; Lee, Jin Yong; Sun, Lixiang

    2016-07-01

    Self-assembly of melamine-cyanuric acid (MC) leads to urinary tract calculi and renal failure. The hydration effects on molecular geometry, the IR spectra, the frontier molecular orbital, the energy barrier of proton transfer (PT), as well as the stability of MC were explored by density functional theory (DFT) calculations. The intramolecular PT breaks the big π-conjugated ring of melamine or converts the p-π conjugation (:N-C'=O) to π-π conjugation (O=C-N=C') of cyanuric acid. The intermolecular PT varies the coupling between melamine and cyanuric acid from pure hydrogen bonds (Na…HNd and NH…O) to the cooperation of cation…anion electrostatic interaction (NaH(+)…Nd (-)) and two NH…O hydrogen bonds. Distinct IR spectra shifts occur for Na…HNd stretching mode upon PT, i.e., blue-shift upon intramolecular PT and red-shift upon intermolecular PT. It is expected that the PT would inhibit the generation of rosette-like structure or one-dimensional tape conformer for the MC complexes. Hydration obviously effects the local geometric structure around the water binding site, as well as the IR spectra of NH…O and N…HN hydrogen bonds. Hydration decreases the intramolecular PT barrier from ~45 kcal mol(-1) in anhydrous complex to ~11.5 kcal mol(-1) in trihydrated clusters. While, the hydration effects on intermolecular PT barrier is slight. The relative stability of MC varies slightly by hydration due to the strong hydrogen bond interaction between melamine and cyanuric acid fragments. Graphical Abstract Hydration effect on proton transfer in melamine-cyanuric acid complex. PMID:27351422

  11. Transfer and distortion of atmospheric information in the satellite temperature retrieval problem

    NASA Technical Reports Server (NTRS)

    Thompson, O. E.

    1981-01-01

    A systematic approach to investigating the transfer of basic ambient temperature information and its distortion by satellite systems and subsequent analysis algorithms is discussed. The retrieval analysis cycle is derived, the variance spectrum of information is examined as it takes different forms in that process, and the quality and quantity of information existing at each stop is compared with the initial ambient temperature information. Temperature retrieval algorithms can smooth, add, or further distort information, depending on how stable the algorithm is, and how heavily influenced by a priori data.

  12. Complexity, parameter sensitivity and parameter transferability in the modelling of floodplain inundation

    NASA Astrophysics Data System (ADS)

    Bates, P. D.; Neal, J. C.; Fewtrell, T. J.

    2012-12-01

    In this we paper we consider two related questions. First, we address the issue of how much physical complexity is necessary in a model in order to simulate floodplain inundation to within validation data error. This is achieved through development of a single code/multiple physics hydraulic model (LISFLOOD-FP) where different degrees of complexity can be switched on or off. Different configurations of this code are applied to four benchmark test cases, and compared to the results of a number of industry standard models. Second we address the issue of how parameter sensitivity and transferability change with increasing complexity using numerical experiments with models of different physical and geometric intricacy. Hydraulic models are a good example system with which to address such generic modelling questions as: (1) they have a strong physical basis; (2) there is only one set of equations to solve; (3) they require only topography and boundary conditions as input data; and (4) they typically require only a single free parameter, namely boundary friction. In terms of complexity required we show that for the problem of sub-critical floodplain inundation a number of codes of different dimensionality and resolution can be found to fit uncertain model validation data equally well, and that in this situation Occam's razor emerges as a useful logic to guide model selection. We find also find that model skill usually improves more rapidly with increases in model spatial resolution than increases in physical complexity, and that standard approaches to testing hydraulic models against laboratory data or analytical solutions may fail to identify this important fact. Lastly, we find that in benchmark testing studies significant differences can exist between codes with identical numerical solution techniques as a result of auxiliary choices regarding the specifics of model implementation that are frequently unreported by code developers. As a consequence, making sound

  13. Disruption of corticocortical information transfer during ketamine anesthesia in the primate brain.

    PubMed

    Schroeder, Karen E; Irwin, Zachary T; Gaidica, Matt; Bentley, J Nicole; Patil, Parag G; Mashour, George A; Chestek, Cynthia A

    2016-07-01

    The neural mechanisms of anesthetic-induced unconsciousness have yet to be fully elucidated, in part because of the diverse molecular targets of anesthetic agents. We demonstrate, using intracortical recordings in macaque monkeys, that information transfer between structurally connected cortical regions is disrupted during ketamine anesthesia, despite preserved primary sensory representation. Furthermore, transfer entropy, an information-theoretic measure of directed connectivity, decreases significantly between neuronal units in the anesthetized state. This is the first direct demonstration of a general anesthetic disrupting corticocortical information transfer in the primate brain. Given past studies showing that more commonly used GABAergic drugs inhibit surrogate measures of cortical communication, this finding suggests the potential for a common network-level mechanism of anesthetic-induced unconsciousness. PMID:27095309

  14. Spectroscopic Structural Investigations of Charge-Transfer Complexes of n-DONORS and - and Pi-Acceptors

    NASA Astrophysics Data System (ADS)

    Nour, El-Metwally; Alqaradawi, Siham Y.

    2009-06-01

    Molecular charge - transfer complexes of n-electron donors such as amines, pyridines and polynitrogen cyclic bases with both sigma- and pi-acceptors have been studied spectrophotometrically in chloroform. The reaction stoichiometries were determined using photometric titration methods. The formed CT-complexes are characterized and formulated based on electronic and infrared spectra as well as elemental and thermal measurements.

  15. A versatile ruthenium(II)-NNC complex catalyst for transfer hydrogenation of ketones and Oppenauer-type oxidation of alcohols.

    PubMed

    Du, Wangming; Wang, Liandi; Wu, Ping; Yu, Zhengkun

    2012-09-10

    A ruthenium(II)-NNC pincer complex containing an unsymmetrical tridentate pyrazolyl-pyridyl-tolyl ligand was synthesized and structually characterized. This complex exhibited excellent catalytic activity for the transfer hydrogenation of ketones in 2-propanol at reflux, and for the Oppenauer-type dehydrogenative oxidation of alcohols in acetone at reflux (see scheme). PMID:22887575

  16. The transfer and transformation of collective network information in gene-matched networks

    PubMed Central

    Kitsukawa, Takashi; Yagi, Takeshi

    2015-01-01

    Networks, such as the human society network, social and professional networks, and biological system networks, contain vast amounts of information. Information signals in networks are distributed over nodes and transmitted through intricately wired links, making the transfer and transformation of such information difficult to follow. Here we introduce a novel method for describing network information and its transfer using a model network, the Gene-matched network (GMN), in which nodes (neurons) possess attributes (genes). In the GMN, nodes are connected according to their expression of common genes. Because neurons have multiple genes, the GMN is cluster-rich. We show that, in the GMN, information transfer and transformation were controlled systematically, according to the activity level of the network. Furthermore, information transfer and transformation could be traced numerically with a vector using genes expressed in the activated neurons, the active-gene array, which was used to assess the relative activity among overlapping neuronal groups. Interestingly, this coding style closely resembles the cell-assembly neural coding theory. The method introduced here could be applied to many real-world networks, since many systems, including human society and various biological systems, can be represented as a network of this type. PMID:26450411

  17. The transfer and transformation of collective network information in gene-matched networks.

    PubMed

    Kitsukawa, Takashi; Yagi, Takeshi

    2015-01-01

    Networks, such as the human society network, social and professional networks, and biological system networks, contain vast amounts of information. Information signals in networks are distributed over nodes and transmitted through intricately wired links, making the transfer and transformation of such information difficult to follow. Here we introduce a novel method for describing network information and its transfer using a model network, the Gene-matched network (GMN), in which nodes (neurons) possess attributes (genes). In the GMN, nodes are connected according to their expression of common genes. Because neurons have multiple genes, the GMN is cluster-rich. We show that, in the GMN, information transfer and transformation were controlled systematically, according to the activity level of the network. Furthermore, information transfer and transformation could be traced numerically with a vector using genes expressed in the activated neurons, the active-gene array, which was used to assess the relative activity among overlapping neuronal groups. Interestingly, this coding style closely resembles the cell-assembly neural coding theory. The method introduced here could be applied to many real-world networks, since many systems, including human society and various biological systems, can be represented as a network of this type. PMID:26450411

  18. An application protocol for CAD to CAD transfer of electronic information

    NASA Technical Reports Server (NTRS)

    Azu, Charles C., Jr.

    1993-01-01

    The exchange of Computer Aided Design (CAD) information between dissimilar CAD systems is a problem. This is especially true for transferring electronics CAD information such as multi-chip module (MCM), hybrid microcircuit assembly (HMA), and printed circuit board (PCB) designs. Currently, there exists several neutral data formats for transferring electronics CAD information. These include IGES, EDIF, and DXF formats. All these formats have limitations for use in exchanging electronic data. In an attempt to overcome these limitations, the Navy's MicroCIM program implemented a project to transfer hybrid microcircuit design information between dissimilar CAD systems. The IGES (Initial Graphics Exchange Specification) format is used since it is well established within the CAD industry. The goal of the project is to have a complete transfer of microelectronic CAD information, using IGES, without any data loss. An Application Protocol (AP) is being developed to specify how hybrid microcircuit CAD information will be represented by IGES entity constructs. The AP defines which IGES data items are appropriate for describing HMA geometry, connectivity, and processing as well as HMA material characteristics.

  19. Hyperbolic mapping of complex networks based on community information

    NASA Astrophysics Data System (ADS)

    Wang, Zuxi; Li, Qingguang; Jin, Fengdong; Xiong, Wei; Wu, Yao

    2016-08-01

    To improve the hyperbolic mapping methods both in terms of accuracy and running time, a novel mapping method called Community and Hyperbolic Mapping (CHM) is proposed based on community information in this paper. Firstly, an index called Community Intimacy (CI) is presented to measure the adjacency relationship between the communities, based on which a community ordering algorithm is introduced. According to the proposed Community-Sector hypothesis, which supposes that most nodes of one community gather in a same sector in hyperbolic space, CHM maps the ordered communities into hyperbolic space, and then the angular coordinates of nodes are randomly initialized within the sector that they belong to. Therefore, all the network nodes are so far mapped to hyperbolic space, and then the initialized angular coordinates can be optimized by employing the information of all nodes, which can greatly improve the algorithm precision. By applying the proposed dual-layer angle sampling method in the optimization procedure, CHM reduces the time complexity to O(n2) . The experiments show that our algorithm outperforms the state-of-the-art methods.

  20. Characterization of DNA/Lipid Complexes by Fluorescence Resonance Energy Transfer

    PubMed Central

    Madeira, Catarina; Loura, Luís M. S.; Aires-Barros, M. Raquel; Fedorov, Aleksander; Prieto, Manuel

    2003-01-01

    Fluorescence resonance energy transfer (FRET) is a potential method for the characterization of DNA-cationic lipid complexes (lipoplexes). In this work, we used FRET models assuming a multilamellar lipoplex arrangement. The application of these models allows the determination of the distance between the fluorescent intercalator on the DNA and a membrane dye on the lipid, and/or the evaluation of encapsulation efficiencies of this liposomal vehicle. The experiments were carried out in 1,2-dioleoyl-3-trimethylammonium-propane/pUC19 complexes with different charge ratios. We used 2-(3-(diphenylhexatrienyl)propanoyl)-1-hexadecanoyl-sn-glycero-3-phosphocholine (DPH-PC) and 2-(4,4-difluoro-5-octyl-4-bora-3a,4a-diaza-s-indacene-3-pentanoyl)-1-hexadecanoyl-sn-glycero-3-phosphocholine (BODIPY-PC) as membrane dyes, and ethidium bromide (EtBr) and BOBO-1 as DNA intercalators. In cationic complexes (charge ratios (+/−) ≥ 2), we verified that BOBO-1 remains bound to DNA, and FRET occurs to the membrane dye. This was also confirmed by anisotropy and lifetime measurements. In complexes with all DNA bound to the lipid (charge ratio (+/−) = 4), we determined 27 Å as the distance between the donor and acceptor planes (half the repeat distance for a multilamellar arrangement). In complexes with DNA unbound to the lipids (charge ratio (+/−) = 0.5 and 2), we calculated the encapsulation efficiencies. The presented FRET methodology is, to our knowledge, the first procedure allowing quantification of lipid-DNA contact. PMID:14581211

  1. Automatically Extracting Information Needs from Complex Clinical Questions

    PubMed Central

    Cao, Yong-gang; Cimino, James J; Ely, John; Yu, Hong

    2010-01-01

    Objective Clinicians pose complex clinical questions when seeing patients, and identifying the answers to those questions in a timely manner helps improve the quality of patient care. We report here on two natural language processing models, namely, automatic topic assignment and keyword identification, that together automatically and effectively extract information needs from ad hoc clinical questions. Our study is motivated in the context of developing the larger clinical question answering system AskHERMES (Help clinicians to Extract and aRrticulate Multimedia information for answering clinical quEstionS). Design and Measurements We developed supervised machine-learning systems to automatically assign predefined general categories (e.g., etiology, procedure, and diagnosis) to a question. We also explored both supervised and unsupervised systems to automatically identify keywords that capture the main content of the question. Results We evaluated our systems on 4,654 annotated clinical questions that were collected in practice. We achieved an F1 score of 76.0% for the task of general topic classification and 58.0% for keyword extraction. Our systems have been implemented into the larger question answering system AskHERMES. Our error analyses suggested that inconsistent annotation in our training data have hurt both question analysis tasks. Conclusion Our systems, available at http://www.askhermes.org, can automatically extract information needs from both short (the number of word tokens <20) and long questions (the number of word tokens >20), and from both well-structured and ill-formed questions. We speculate that the performance of general topic classification and keyword extraction can be further improved if consistently annotated data are made available. PMID:20670693

  2. Synergistic oxygen atom transfer by ruthenium complexes with non-redox metal ions.

    PubMed

    Lv, Zhanao; Zheng, Wenrui; Chen, Zhuqi; Tang, Zhiming; Mo, Wanling; Yin, Guochuan

    2016-07-28

    Non-redox metal ions can affect the reactivity of active redox metal ions in versatile biological and heterogeneous oxidation processes; however, the intrinsic roles of these non-redox ions still remain elusive. This work demonstrates the first example of the use of non-redox metal ions as Lewis acids to sharply improve the catalytic oxygen atom transfer efficiency of a ruthenium complex bearing the classic 2,2'-bipyridine ligand. In the absence of Lewis acid, the oxidation of ruthenium(ii) complex by PhI(OAc)2 generates the Ru(iv)[double bond, length as m-dash]O species, which is very sluggish for olefin epoxidation. When Ru(bpy)2Cl2 was tested as a catalyst alone, only 21.2% of cyclooctene was converted, and the yield of 1,2-epoxycyclooctane was only 6.7%. As evidenced by electronic absorption spectra and EPR studies, both the oxidation of Ru(ii) by PhI(OAc)2 and the reduction of Ru(iv)[double bond, length as m-dash]O by olefin are kinetically slow. However, adding non-redox metal ions such as Al(iii) can sharply improve the oxygen transfer efficiency of the catalyst to 100% conversion with 89.9% yield of epoxide under identical conditions. Through various spectroscopic characterizations, an adduct of Ru(iv)[double bond, length as m-dash]O with Al(iii), Ru(iv)[double bond, length as m-dash]O/Al(iii), was proposed to serve as the active species for epoxidation, which in turn generated a Ru(iii)-O-Ru(iii) dimer as the reduced form. In particular, both the oxygen transfer from Ru(iv)[double bond, length as m-dash]O/Al(iii) to olefin and the oxidation of Ru(iii)-O-Ru(iii) back to the active Ru(iv)[double bond, length as m-dash]O/Al(iii) species in the catalytic cycle can be remarkably accelerated by adding a non-redox metal, such as Al(iii). These results have important implications for the role played by non-redox metal ions in catalytic oxidation at redox metal centers as well as for the understanding of the redox mechanism of ruthenium catalysts in the oxygen atom

  3. A charge transfer complex nematic liquid crystalline gel with high electrical conductivity

    NASA Astrophysics Data System (ADS)

    Bhargavi, R.; Nair, Geetha G.; Krishna Prasad, S.; Majumdar, R.; Bag, Braja G.

    2014-10-01

    We describe the rheological, dielectric and elastic properties of a nematic liquid crystal gel created using an anthrylidene derivative of arjunolic acid, a chiral triterpenoid, obtained from the extracts of the wood of Terminalia arjuna. In this novel gel, having the electron-donor and acceptor components as minority constituents, the gelation and strengthening of charge-transfer complex (CTC) formation are seen to be occurring concomitantly. In addition to being mechanically strong with a large storage modulus, the gel with the maximized CTC exhibits Frank bend elastic constant values that approach nanonewton levels. The highlight of the study is the observation of 4-5 orders of magnitude increase in electrical conductivity for this gel, a value that is higher than even in the CT complexes of 2-d ordered columnar structures. A further important advantage of the present system over the columnar complex is that the high conductivity is seen for ac probing also, and owing to the nematic nature can be switched between its anisotropic limits. Some of these features are ascribed to a specific molecular packing architecture, which reduces the trapping of the charge carriers.

  4. Charge-transfer complexes of 1-(2-aminoethyl) piperazine with σ- and π-acceptors

    NASA Astrophysics Data System (ADS)

    Mostafa, Adel; Bazzi, Hassan S.

    2010-11-01

    The solid charge-transfer (CT) molecular complexes formed in the reaction of 1-(2-aminoethyl) piperazine (AEPIP) with the σ-acceptor iodine and π-acceptors 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), 7,7,8,8-tetracyanoquinodi-methane (TCNQ), 2,4,4,6-tetrabromo-2,5-cyclohexadienone (TBCHD) and 2,3,5,6-tetrachloro-1,4-benzoquinone (CHL) were studied in chloroform at 25 °C. The products were investigated through electronic and infrared spectra as well as elemental analysis. The obtained results showed that the formed solid CT-complexes have the formulas [(AEPIP) I] +I5-, [(AEPIP)(DDQ) 2], [(AEPIP)(TCNQ) 2], [(AEPIP) 2(TBCHD) 3] and [(AEPIP)(CHL)] which are in full agreement with the known reaction stoichiometries in solution as well as the elemental analysis measurements. The formation constant KCT, molar extinction coefficient ɛCT, free energy change Δ G0 and CT energy ECT have been calculated for the CT-complexes [(AEPIP)(DDQ) 2], [(AEPIP)(TCNQ) 2] and [(AEPIP)(CHL)] as well.

  5. Charge-transfer complexes of 4-methylpiperidine with σ- and π-acceptors

    NASA Astrophysics Data System (ADS)

    AlQaradawi, Siham Y.; Mostafa, Adel; Bazzi, Hassan S.

    2015-01-01

    The solid charge-transfer (CT) molecular complexes formed in the reaction of the electron donor 4-methylpiperidine (4MP) with the σ-electron acceptor iodine and π-acceptors 7,7,8,8-tetracyanoquinodimethane (TCNQ), 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) and 2,4,4,6-tetrabromo-2,5-cyclohexadienone (TBCHD) have been investigated spectrophotometrically in chloroform at 25 °C. These were characterized through electronic and infrared spectra as well as elemental and thermal analysis. The obtained results showed that the formed solid CT-complexes have the formulas [(4MP) I]+I-3, [(4MP)(DDQ)2] and [(4MP)(TBCHD)] and with TCNQ the adduct [TCMPQDM] is obtained through N-substitution reaction in full agreement with the known reaction stoichiometries in solution as well as the elemental measurements. The formation constant KCT, molar extinction coefficient εCT, free energy change ΔG0, CT energy ECT and the ionization potential Ip have been calculated for the CT-complexes [(4MP) I]+I-3, [(4MP)(DDQ)2] and [(4MP)(TBCHD)].

  6. Drop formation, pinch-off dynamics and liquid transfer of simple and complex fluids

    NASA Astrophysics Data System (ADS)

    Dinic, Jelena; Sharma, Vivek

    Liquid transfer and drop formation processes underlying jetting, spraying, coating, and printing - inkjet, screen, roller-coating, gravure, nanoimprint hot embossing, 3D - often involve formation of unstable columnar necks. Capillary-driven thinning of such necks and their pinchoff dynamics are determined by a complex interplay of inertial, viscous and capillary stresses for simple, Newtonian fluids. Micro-structural changes in response to extensional flow field that arises within the thinning neck give rise to additional viscoelastic stresses in complex, non- Newtonian fluids. Using FLOW-3D, we simulate flows realized in prototypical geometries (dripping and liquid bridge stretched between two parallel plates) used for studying pinch-off dynamics and influence of microstructure and viscoelasticity. In contrast with often-used 1D or 2D models, FLOW-3D allows a robust evaluation of the magnitude of the underlying stresses and extensional flow field (both uniformity and magnitude). We find that the simulated radius evolution profiles match the pinch-off dynamics that are experimentally-observed and theoretically-predicted for model Newtonian fluids and complex fluids.

  7. Disturbed excitation energy transfer in Arabidopsis thaliana mutants lacking minor antenna complexes of photosystem II.

    PubMed

    Dall'Osto, Luca; Ünlü, Caner; Cazzaniga, Stefano; van Amerongen, Herbert

    2014-12-01

    Minor light-harvesting complexes (Lhcs) CP24, CP26 and CP29 occupy a position in photosystem II (PSII c' plants between the major light-harvesting complexes LHCII and the PSII core subunits. Lack of minor Lhcs in vivo causes impairment of PSII organization, and negatively affects electron transport rates anc photoprotection capacity. Here we used picosecond-fluorescence spectroscopy to study excitation-energy transfer (EET) in thylakoid membranes isolated from Arabidopsis thaliana wild-type plants and knockout lines depleted of either two (koCP26/24 and koCP29/24) or all minor Lhcs (NoM). In the absence of all minor Lhcs. the functional connection ofLHCII to the PSII cores appears to be seriously impaired whereas the "disconnected" LHCII is substantially quenched. For both double knock-out mutants, excitation trapping in PSII is faster than in NoM thylakoids but slower than in WT thylakoids. In NoM thylakoids, the loss of all minor Lhcs is accompanied by an over-accumulation ofLHCII, suggesting a compensating response to the reduced trapping efficiency in limiting light, which leads to a photosynthetic phenotype resembling that of low-light-acclimated plants. Finally. fluorescence kinetics and biochemical results show that the missing minor complexes are not replaced by other Lhcs, implying that they are unique among the antenna subunits and crucial for the functioning and macroorganization of PSII. PMID:25291424

  8. A charge transfer complex nematic liquid crystalline gel with high electrical conductivity

    SciTech Connect

    Bhargavi, R.; Nair, Geetha G. E-mail: skpras@gmail.com; Krishna Prasad, S. E-mail: skpras@gmail.com; Majumdar, R.; Bag, Braja G.

    2014-10-21

    We describe the rheological, dielectric and elastic properties of a nematic liquid crystal gel created using an anthrylidene derivative of arjunolic acid, a chiral triterpenoid, obtained from the extracts of the wood of Terminalia arjuna. In this novel gel, having the electron-donor and acceptor components as minority constituents, the gelation and strengthening of charge-transfer complex (CTC) formation are seen to be occurring concomitantly. In addition to being mechanically strong with a large storage modulus, the gel with the maximized CTC exhibits Frank bend elastic constant values that approach nanonewton levels. The highlight of the study is the observation of 4–5 orders of magnitude increase in electrical conductivity for this gel, a value that is higher than even in the CT complexes of 2-d ordered columnar structures. A further important advantage of the present system over the columnar complex is that the high conductivity is seen for ac probing also, and owing to the nematic nature can be switched between its anisotropic limits. Some of these features are ascribed to a specific molecular packing architecture, which reduces the trapping of the charge carriers.

  9. Quasi-analytical treatment of spatially averaged radiation transfer in complex terrain

    NASA Astrophysics Data System (ADS)

    Löwe, H.; Helbig, N.

    2012-04-01

    We provide a new quasi-analytical method to compute the topographic influence on the effective albedo of complex topography as required for meteorological, land-surface or climate models. We investigate radiative transfer in complex terrain via the radiosity equation on isotropic Gaussian random fields. Under controlled approximations we derive expressions for domain averages of direct, diffuse and terrain radiation and the sky view factor. Domain averaged quantities are related to a type of level-crossing probability of the random field which is approximated by longstanding results developed for acoustic scattering at ocean boundaries. This allows us to express all non-local horizon effects in terms of a local terrain parameter, namely the mean squared slope. Emerging integrals are computed numerically and fit formulas are given for practical purposes. As an implication of our approach we provide an expression for the effective albedo of complex terrain in terms of the sun elevation angle, mean squared slope, the area averaged surface albedo, and the direct-to-diffuse ratio of solar radiation. As an application, we compute the effective albedo for the Swiss Alps and discuss possible generalizations of the method.

  10. Quasi-analytical treatment of spatially averaged radiation transfer in complex terrain

    NASA Astrophysics Data System (ADS)

    LöWe, H.; Helbig, N.

    2012-10-01

    We provide a new quasi-analytical method to compute the subgrid topographic influences on the shortwave radiation fluxes and the effective albedo in complex terrain as required for large-scale meteorological, land surface, or climate models. We investigate radiative transfer in complex terrain via the radiosity equation on isotropic Gaussian random fields. Under controlled approximations we derive expressions for domain-averaged fluxes of direct, diffuse, and terrain radiation and the sky view factor. Domain-averaged quantities can be related to a type of level-crossing probability of the random field, which is approximated by long-standing results developed for acoustic scattering at ocean boundaries. This allows us to express all nonlocal horizon effects in terms of a local terrain parameter, namely, the mean-square slope. Emerging integrals are computed numerically, and fit formulas are given for practical purposes. As an implication of our approach, we provide an expression for the effective albedo of complex terrain in terms of the Sun elevation angle, mean-square slope, the area-averaged surface albedo, and the ratio of atmospheric direct beam to diffuse radiation. For demonstration we compute the decrease of the effective albedo relative to the area-averaged albedo in Switzerland for idealized snow-covered and clear-sky conditions at noon in winter. We find an average decrease of 5.8% and spatial patterns which originate from characteristics of the underlying relief. Limitations and possible generalizations of the method are discussed.

  11. The reaction of an iridium PNP complex with parahydrogen facilitates polarisation transfer without chemical change† †Electronic supplementary information (ESI) available: Sample preparation, signal enhancements and raw data. CCDC 1026865. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c4dt03088e Click here for additional data file. Click here for additional data file.

    PubMed Central

    Holmes, Arthur J.; Rayner, Peter J.; Cowley, Michael J.; Green, Gary G. R.; Whitwood, Adrian C.

    2015-01-01

    The short lived pincer complex [(C5H3N(CH2P(tBu)2)2)Ir(H)2(py)]BF4 is shown to be active for signal amplification by reversible exchange. This catalyst formulation enables the efficient transfer of polarization from parahydrogen to be placed into just a single molecule of the hyperpolarisation target, pyridine. When the catalysts 1H nuclei are replaced by 2H, increased levels of substrate hyperpolarization result and when the reverse situation is examined the catalyst itself is clearly visible through hyperpolarised signals. The ligand exchange pathways of [(C5H3N(CH2P(tBu)2)2)Ir(H)2(py)]BF4 that are associated with this process are shown to involve the formation of 16-electron [(C5H3N(CH2P(tBu)2)2)Ir(H)2]BF4 and the 18-electron H2 addition product [(C5H3N(CH2P(tBu)2)2)Ir(H)2(H2)]BF4. PMID:25410259

  12. Long-distance quantum information transfer with strong coupling hybrid solid system

    PubMed Central

    Zhang, Feng-Yang; Chen, Xin-Yu; Li, Chong; Song, He-Shan

    2015-01-01

    In this paper, we demonstrate how information can be transferred among the long-distance memory units in a hybrid solid architecture, which consists the nitrogen-vacancy (NV) ensemble acting as the memory unit, the LC circuit acting as the transmitter (receiver), and the flux qubit acting as the interface. Numerical simulation demonstrates that the high-fidelity quantum information transfer between memory unit and transmitter (receiver) can be implemented, and this process is robust to both the LC circuit decay and NV ensemble spontaneous emission. PMID:26585779

  13. Quantum Oblivious Transfer Based on a Quantum Symmetrically Private Information Retrieval Protocol

    NASA Astrophysics Data System (ADS)

    Yang, Yu-Guang; Sun, Si-Jia; Wang, Yan

    2015-03-01

    Private information retrieval implies oblivious transfer in classical cryptography. Following this clue, we present a novel quantum one-out-of-two OT protocol based on a practical quantum symmetrically private information retrieval protocol Jakobi et al. (Phys. Rev. A 83, 022301 2011), with changes only in the classical postprocessing of the key. While unconditionally secure oblivious transfer is known to be impossible, we argue that an interesting degree of security can be achieved by means of quantum physical principles instead of unproven security assumptions in order to protect both the sender and the receiver. The proposed OT protocol is loss tolerant, practical and robust against quantum memory attack.

  14. Quantum-information transfer with nitrogen-vacancy centers coupled to a whispering-gallery microresonator

    SciTech Connect

    Li Pengbo; Gao Shaoyan; Li Fuli

    2011-05-15

    We propose an efficient scheme for the realization of quantum information transfer and entanglement with nitrogen-vacancy (N-V) centers coupled to a high-Q whispering-gallery mode (WGM) microresonator. We show that based on the effective dipole-dipole interaction between the N-V centers mediated by the WGM, quantum information can be transferred between the N-V centers through Raman transitions combined with laser fields. This protocol may open up promising possibilities for quantum communications with the solid-state quantum electrodynamic cavity system.

  15. Long-distance quantum information transfer with strong coupling hybrid solid system

    NASA Astrophysics Data System (ADS)

    Zhang, Feng-Yang; Chen, Xin-Yu; Li, Chong; Song, He-Shan

    2015-11-01

    In this paper, we demonstrate how information can be transferred among the long-distance memory units in a hybrid solid architecture, which consists the nitrogen-vacancy (NV) ensemble acting as the memory unit, the LC circuit acting as the transmitter (receiver), and the flux qubit acting as the interface. Numerical simulation demonstrates that the high-fidelity quantum information transfer between memory unit and transmitter (receiver) can be implemented, and this process is robust to both the LC circuit decay and NV ensemble spontaneous emission.

  16. Pincer-Type Complexes for Catalytic (De)Hydrogenation and Transfer (De)Hydrogenation Reactions: Recent Progress.

    PubMed

    Werkmeister, Svenja; Neumann, Jacob; Junge, Kathrin; Beller, Matthias

    2015-08-24

    Pincer complexes are becoming increasingly important for organometallic chemistry and organic synthesis. Since numerous applications for such catalysts have been developed in recent decades, this Minireview covers progress in their use as catalysts for (de)hydrogenation and transfer (de)hydrogenation reactions during the last four years. Aside from noble-metal-based pincer complexes, the corresponding base metal complexes are also highlighted and their applications summarized. PMID:26179375

  17. Entropy-Based Analysis and Bioinformatics-Inspired Integration of Global Economic Information Transfer

    PubMed Central

    An, Sungbae; Kwon, Young-Kyun; Yoon, Sungroh

    2013-01-01

    The assessment of information transfer in the global economic network helps to understand the current environment and the outlook of an economy. Most approaches on global networks extract information transfer based mainly on a single variable. This paper establishes an entirely new bioinformatics-inspired approach to integrating information transfer derived from multiple variables and develops an international economic network accordingly. In the proposed methodology, we first construct the transfer entropies (TEs) between various intra- and inter-country pairs of economic time series variables, test their significances, and then use a weighted sum approach to aggregate information captured in each TE. Through a simulation study, the new method is shown to deliver better information integration compared to existing integration methods in that it can be applied even when intra-country variables are correlated. Empirical investigation with the real world data reveals that Western countries are more influential in the global economic network and that Japan has become less influential following the Asian currency crisis. PMID:23300959

  18. Information, the decision forum, and third-party effects in water transfers

    NASA Astrophysics Data System (ADS)

    Nunn, Susan Christopher; Ingram, Helen M.

    1988-04-01

    Transfers of water from irrigation to municipal and industrial uses are seen as a low-cost approach to the water supply problems of western cities. Rural areas of origin protest that market transfers ignore indirect economic, political, social, fiscal, and environmental effects of changes in water use. The capacity of five different water transfer institutions: the market, courts, legislature, special purpose districts, and administrative agencies, to develop and weigh information about indirect and nonuser impacts is analyzed and compared. All five forums are found to have biases regarding the type of information used. Markets process information on direct economic costs and benefits well but ignore third-party costs; legislative bodies are sensitive to information about indirect and nonuser impacts but distort information on direct benefits and costs; neither the judiciary nor the water agency is likely to consider community and social impacts of water transfers. Special districts could consider both direct and indirect values but are often controlled by a leadership elite, pursuing narrow goals with minimum membership participation. The appropriate forum for decision making depends upon our priorities among values and on the values that are at stake in particular issues.

  19. Entropy-based analysis and bioinformatics-inspired integration of global economic information transfer.

    PubMed

    Kim, Jinkyu; Kim, Gunn; An, Sungbae; Kwon, Young-Kyun; Yoon, Sungroh

    2013-01-01

    The assessment of information transfer in the global economic network helps to understand the current environment and the outlook of an economy. Most approaches on global networks extract information transfer based mainly on a single variable. This paper establishes an entirely new bioinformatics-inspired approach to integrating information transfer derived from multiple variables and develops an international economic network accordingly. In the proposed methodology, we first construct the transfer entropies (TEs) between various intra- and inter-country pairs of economic time series variables, test their significances, and then use a weighted sum approach to aggregate information captured in each TE. Through a simulation study, the new method is shown to deliver better information integration compared to existing integration methods in that it can be applied even when intra-country variables are correlated. Empirical investigation with the real world data reveals that Western countries are more influential in the global economic network and that Japan has become less influential following the Asian currency crisis. PMID:23300959

  20. To Transfer or Not to Transfer? Development of a Dinitrosyl Iron Complex as a Nitroxyl Donor for the Nitroxylation of an Fe(III) -Porphyrin Center.

    PubMed

    Tseng, Yu-Ting; Chen, Chien-Hong; Lin, Jing-Yu; Li, Bing-Han; Lu, Yu-Huan; Lin, Chia-Her; Chen, Hsin-Tsung; Weng, Tsu-Chien; Sokaras, Dimosthenes; Chen, Huang-Yeh; Soo, Yun-Liang; Lu, Tsai-Te

    2015-12-01

    A positive myocardial inotropic effect achieved using HNO/NO(-) , compared with NO⋅, triggered attempts to explore novel nitroxyl donors for use in clinical applications in vascular and myocardial pharmacology. To develop M-NO complexes for nitroxyl chemistry and biology, modulation of direct nitroxyl-transfer reactivity of dinitrosyl iron complexes (DNICs) is investigated in this study using a Fe(III) -porphyrin complex and proteins as a specific probe. Stable dinuclear {Fe(NO)2 }(9) DNIC [Fe(μ-(Me) Pyr)(NO)2 ]2 was discovered as a potent nitroxyl donor for nitroxylation of Fe(III) -heme centers through an associative mechanism. Beyond the efficient nitroxyl transfer, transformation of DNICs into a chemical biology probe for nitroxyl and for pharmaceutical applications demands further efforts using in vitro/in vivo studies. PMID:26437878

  1. Structure determination of chemisorbed chirality transfer complexes: Accelerated STM analysis and exchange-correlation functional sensitivity

    NASA Astrophysics Data System (ADS)

    Groves, M. N.; Goubert, G.; Rasmussen, A. M. H.; Dong, Y.; Lemay, J.-C.; Demers-Carpentier, V.; McBreen, P. H.; Hammer, B.

    2014-11-01

    Linking STM images to atomic positions determined by DFT calculations is an important step in characterizing the intermolecular interactions at play in many surface processes including asymmetric hydrogenation on heterogeneous catalysts. An accelerated data extraction method is used to collect STM information on the geometry of complexes formed between the two substrates, 2,2,2-trifluoroacetophenone (TFAP) and 3,3,3-methyltrifluoropyruvate (MTFP), and the chiral modifier (R)-(+)-1-(1-naphthyl)ethylamine ((R)-NEA) on Pt(111). We present new experimental data for complexes formed by MTFP and the (R)-NEA-1 conformer along with a new and enlarged set of reformulated STM data that extends what was reported in previously published studies of complexed MTFP and TFAP. Atomic geometries based on DFT calculations using PBE, M06-L, and optB88-vdW exchange-correlation functionals will also be presented. It will be shown that both substrates have well-defined complexation geometries when interacting with the modifier and that the relative complexation energies are not markedly sensitive to the functional employed.

  2. Comparison of DNA-lipid complexes and DNA alone for gene transfer to cystic fibrosis airway epithelia in vivo.

    PubMed Central

    Zabner, J; Cheng, S H; Meeker, D; Launspach, J; Balfour, R; Perricone, M A; Morris, J E; Marshall, J; Fasbender, A; Smith, A E; Welsh, M J

    1997-01-01

    Cationic lipids show promise as vectors for transfer of CFTR cDNA to airway epithelia of patients with cystic fibrosis (CF). However, previous studies have not compared the effect of DNA-lipid to DNA alone. Recently, we developed a formulation of plasmid encoding CFTR (pCF1-CFTR) and cationic lipid (GL-67:DOPE) that generated greater gene transfer in mouse lung than previously described DNA-lipid vectors. Therefore, we tested the hypothesis that DNA-lipid complexes were more effective than DNA alone at transferring CFTR cDNA to airway epithelia in vivo. We administered complexes of DNA-lipid to one nostril and DNA alone to the other nostril in a randomized, double-blind study. Electrophysiologic measurements showed that DNA-lipid complexes partially corrected the Cl- transport defect. Importantly, the pCF1-CFTR plasmid alone was at least as effective as complexes of DNA with lipid. Measurements of vector-specific CFTR transcripts also showed gene transfer with both DNA-lipid and DNA alone. These results indicate that nonviral vectors can transfer CFTR cDNA to airway epithelia and at least partially restore the Cl- transport defect characteristic of CF. However, improvements in the overall efficacy of gene transfer are required to develop a treatment for CF. PMID:9294121

  3. Direct observation of ultrafast energy-transfer processes in light harvesting complex II

    SciTech Connect

    Du, M.; Mets, L.; Fleming, G.R. ); Xie, X. Pacific Northwest Lab., Richland, WA )

    1994-04-28

    A femtosecond fluorescence upconversion apparatus was used to study the isotropic and anisotropic fluorescence dynamics in the chlorophyll a/b light harvesting complex II of a PS I-PS II double-efficiency strain, C2, of Chlamydomonas reinhardtii. The fluorescence depolarization measurements reveal nonexponential behavior that is well described by a sum of two exponentials with time constants of 250-300 fs and 5-12 ps. The nonexponential behavior likely arises from intracomplex heterogeneity in the structural and spectral factors that nonexponential behavior likely arises from intracomplex heterogeneity in the structural and spectral factors that control energy-transfer dynamics. Isotropic fluorescence measurements reveal a rise time of 250-300 fs at both 700 and 710 nm, but not at 730 nm. We discuss the implications of our data for LHC II structural organization. 36 refs., 4 figs., 1 tab.

  4. Iodine-polyphenylacetylene charge-transfer complex: an ab initio quantum-chemical assessment

    NASA Astrophysics Data System (ADS)

    Andreocci, M. V.; Bossa, M.; Furlani, A.; Polzonetti, G.; Russo, M. V.

    1991-07-01

    The ab initio MO-LCAO-HF method has been used to calculate the electronic structure of the iodine-polyphenylacetylene charge-transfer complex (PPAI 2). Two models have been considered for the PPA molecule: a simple one containing two phenyl groups and a more realistic one containing six phenyl groups. The calculations give automatically the charge separation between I 5 and the polymer, and show that the total charge separation can be less than 1 e at short distances. The computed charges at the energy minimum have been succesfully introduced into the curve fitting of the I-3d 5/2 core level spectrum of PPAI 2 films, giving good agreement between experimental and theoretical results.

  5. Photoinduced electron transfer and fluorescence mechanisms in covalently linked polynuclear aromatic-nucleotide complexes

    SciTech Connect

    Geacintov, N.E.; Mao, Bing; Zhao, Rushen; Chen, Junxin; Liu, Tong Ming; Ya, Nai-Qi; France, L.L.; Sutherland, J.D.

    1992-04-01

    The fluorescence of polycyclic aromatic hydrocarbon-nucleic acid complexes is quenched by photoinduced electron transfer mechanisms in aqueous solutions at ambient temperatures. These effects are illustrated with the biologically important compound benzo[a]pyrene-7,8-diol-9,10-epoxide (BPDE), a mutagenic and carcinogenic metabolite of the environmental pollutant benzo[a]pyrene, which forms covalent mutagenic lesions with 2{prime}-deoxyguanosine (dG) residues in DNA. The dependence of the fluroescence yeild and fluorescence decay times of the covalent model adduct (+)-trans-BPDE-N{sup 2}-dG as a function of temperature and methanol/water composition are described. Because of the sensitivity of the fluorescence of the pyrenyl residue to the polarity of the microenvironment, the magnitude of the fluorescence yield can be used to distinguish between highly hydrophobic (e.g. intercalation) and other more solvent-exposed BPDE-nucleic acid binding sites.

  6. Photoinduced electron transfer and fluorescence mechanisms in covalently linked polynuclear aromatic-nucleotide complexes

    SciTech Connect

    Geacintov, N.E.; Mao, Bing; Zhao, Rushen; Chen, Junxin; Liu, Tong Ming; Ya, Nai-Qi . Dept. of Chemistry); France, L.L.; Sutherland, J.D. )

    1992-01-01

    The fluorescence of polycyclic aromatic hydrocarbon-nucleic acid complexes is quenched by photoinduced electron transfer mechanisms in aqueous solutions at ambient temperatures. These effects are illustrated with the biologically important compound benzo(a)pyrene-7,8-diol-9,10-epoxide (BPDE), a mutagenic and carcinogenic metabolite of the environmental pollutant benzo(a)pyrene, which forms covalent mutagenic lesions with 2{prime}-deoxyguanosine (dG) residues in DNA. The dependence of the fluroescence yeild and fluorescence decay times of the covalent model adduct (+)-trans-BPDE-N{sup 2}-dG as a function of temperature and methanol/water composition are described. Because of the sensitivity of the fluorescence of the pyrenyl residue to the polarity of the microenvironment, the magnitude of the fluorescence yield can be used to distinguish between highly hydrophobic (e.g. intercalation) and other more solvent-exposed BPDE-nucleic acid binding sites.

  7. An infrared thermography imaging system for convective heat transfer measurements in complex flows

    NASA Astrophysics Data System (ADS)

    Sargent, S. R.; Hedlund, C. R.; Ligrani, P. M.

    1998-12-01

    An infrared thermography imaging system is described for spatially resolved convective heat transfer measurements when used in conjunction with thermocouples, energy balances, digital image processing, zinc-selenide windows, and unique in situ calibration procedures. The usefulness of the system and the techniques developed are demonstrated by measurements made in two different environments with complex, three-dimensional flow features. First, spatial variations of surface Nusselt numbers are measured along the concave surfaces of a swirl chamber whose geometry models an internal passage used to cool the leading edge of a turbine blade. Second, spatially resolved distributions of the adiabatic film-cooling effectiveness are measured downstream of film-cooling holes on a symmetric turbine blade in transonic flow.

  8. Gaussian free-energy dependence of electron-transfer rates in iridium complexes

    SciTech Connect

    Fox, L.S.; Gray, H.B. ); Kozik, M.; Winkler, J.R. )

    1990-03-02

    The kinetics of photoinduced electron-transfer (ET) reactions have been measured in a series of synthetic donor-acceptor complexes. The electron donors are singlet or triplet excited iridium(I) dimers (Ir{sub 2}), and the acceptors are N-alkylpyridinium groups covalently bound to phosphinite ligands on the Ir{sub 2} core. Rate constants for excited-state ET range from 3.5 {times} 10{sup 6} to 1.1 {times} 10{sup 11} per second, and thermal back ET (pyridinium radical to Ir{sub 2}{sup +}) rates vary from 2.0 {times} 10{sup 10} to 6.7 {times} 10{sup 7} per second. The variation of these rates with driving force is in remarkably good agreement with the Marcus theory prediction of a Gaussian free-energy dependence. 26 refs., 2 figs., 2 tabs.

  9. Efficient positioning of absorbing material in complex systems by using the Patch Transfer Function method

    NASA Astrophysics Data System (ADS)

    Totaro, N.; Guyader, J. L.

    2012-06-01

    Given the need to decrease energy consumption in the automobile industry, vehicle weight has become an important issue. Regarding acoustic comfort, the weight of noise reduction devices must be minimized inside vehicle compartments. Consequently, these devices, for example those using poro-elastic materials, must be designed carefully to maximize their influence on noise reduction. The present paper describes a method developed to obtain an efficient positioning of a given surface (or mass) of absorbing material characterized by its surface impedance. This technique is based on the Patch Transfer Function method used to couple complex vibro-acoustic sub-domains and which has been successfully applied in the European ViSPeR and Silence projects. First, a numerical analysis of the possibilities of this method is performed on a non-rectangular cavity with rigid walls after which an experimental validation of this numerical analysis is performed to evaluate the accuracy of the method under real conditions.

  10. Charge transfer complex states in diketopyrrolopyrrole polymers and fullerene blends: Implications for organic solar cell efficiency

    NASA Astrophysics Data System (ADS)

    Moghe, D.; Yu, P.; Kanimozhi, C.; Patil, S.; Guha, S.

    2011-12-01

    The spectral photocurrent characteristics of two donor-acceptor diketopyrrolopyrrole (DPP)-based copolymers (PDPP-BBT and TDPP-BBT) blended with a fullerene derivative [6,6]-phenyl C61-butyric acid methyl ester (PCBM) were studied using Fourier-transform photocurrent spectroscopy (FTPS) and monochromatic photocurrent (PC) method. PDPP-BBT:PCBM shows the onset of the lowest charge transfer complex (CTC) state at 1.42 eV, whereas TDPP-BBT:PCBM shows no evidence of the formation of a midgap CTC state. The FTPS and PC spectra of P3HT:PCBM are also compared. The larger singlet state energy difference of TDPP-BBT and PCBM compared to PDPP-BBT/P3HT and PCBM obliterates the formation of a midgap CTC state resulting in an enhanced photovoltaic efficiency over PDPP-BBT:PCBM.

  11. Modeling Electronic-Nuclear Interactions for Excitation Energy Transfer Processes in Light-Harvesting Complexes.

    PubMed

    Lee, Mi Kyung; Coker, David F

    2016-08-18

    An accurate approach for computing intermolecular and intrachromophore contributions to spectral densities to describe the electronic-nuclear interactions relevant for modeling excitation energy transfer processes in light harvesting systems is presented. The approach is based on molecular dynamics (MD) calculations of classical correlation functions of long-range contributions to excitation energy fluctuations and a separate harmonic analysis and single-point gradient quantum calculations for electron-intrachromophore vibrational couplings. A simple model is also presented that enables detailed analysis of the shortcomings of standard MD-based excitation energy fluctuation correlation function approaches. The method introduced here avoids these problems, and its reliability is demonstrated in accurate predictions for bacteriochlorophyll molecules in the Fenna-Matthews-Olson pigment-protein complex, where excellent agreement with experimental spectral densities is found. This efficient approach can provide instantaneous spectral densities for treating the influence of fluctuations in environmental dissipation on fast electronic relaxation. PMID:27472379

  12. Fault-patch stress-transfer efficiency in presence of sub-patch geometric complexity

    NASA Astrophysics Data System (ADS)

    Zielke, Olaf; Mai, Martin

    2015-04-01

    It is well known that faults are not planar surfaces. Instead they exhibit self-similar or self-affine properties that span a wide range of spatial (sub-micrometer to tens-of-kilometer). This geometric fault roughness has a distinct impact on amount and distribution of stresses/strains induced in the medium and on other portions of the fault. However, when numerically simulated (for example in multi-cycle EQ rupture simulations or Coulomb failure stress calculations) this roughness is largely ignored: individual fault patches --the incremental elements that build the fault surface in the respective computer models-- are planar and fault roughness at this and lower spatial scales is not considered. As a result, the fault-patch stress-transfer efficiency may be systematically too large in those numerical simulations with respect to the "actual" efficiency level. Here, we investigate the effect of sub-patch geometric complexity on fault-patch stress-transfer efficiency. For that, we sub-divide a fault patch (e.g., 1x1km) into a large number of sub-patches (e.g., 20x20m) and determine amount of induced stresses at selected positions around that patch for different levels and realizations of fault roughness. For each fault roughness level, we compute mean and standard deviation of the induced stresses, enabling us to compute the coefficient of variation. We normalize those values with stresses from the corresponding single (planar) fault patch, providing scaling factors and their variability for stress transfer efficiency. Given a certain fault roughness that is assumed for a fault, this work provides the means to implement the sub-patch fault roughness into investigations based on fault-patch interaction schemes.

  13. Mechanism of inner-sphere electron transfer via charge-transfer (precursor) complexes. Redox energetics of aromatic donors with the nitrosonium acceptor.

    PubMed

    Rosokha, S V; Kochi, J K

    2001-09-19

    Spontaneous formation of colored (1:1) complexes of various aromatic donors (ArH) with the nitrosonium acceptor (NO+) is accompanied by the appearance of two new (charge-transfer) absorption bands in the UV-vis spectrum. IR spectral and X-ray crystallographic analyses of the [ArH,NO+] complexes reveal their inner-sphere character by the ArH/NO+ separation that is substantially less than the van der Waals contact and by the significant enlargement of the aromatic chromophore. The reversible interchange between such an inner-sphere complex [ArH,NO+] and the redox product (ArH+.+ NO.) is quantitatively assessed for the first time to establish it as the critical intermediate in the overall electron-transfer process. Theoretical formulation of the NO+ binding to ArH is examined by LCAO-MO methodology sufficient to allow the unambiguous assignment of the pair of diagnostic (UV-vis) spectral bands. The MO treatment also provides quantitative insight into the high degree of charge-transfer extant in these inner-sphere complexes as a function of the HOMO-LUMO gap for the donor/acceptor pair. The relative stabilization of [ArH,NO+] is traced directly to the variation in the electronic coupling element H(AB), which is found to be substantially larger than the reorganization energy (lambda/2). In Sutin's development of Marcus-Hush theory, this inequality characterizes a completely delocalized Class III complex (which occupies a single potential well) according to the Robin-Day classification. The mechanistic relevance of such an unusual (precursor) complex to the inner-sphere mechanism for organic electron transfer is discussed. PMID:11552806

  14. Synthesis and Hydride Transfer Reactions of Cobalt and Nickel Hydride Complexes to BX3 Compounds

    SciTech Connect

    Mock, Michael T.; Potter, Robert G.; O'Hagan, Molly J.; Camaioni, Donald M.; Dougherty, William G.; Kassel, W. S.; DuBois, Daniel L.

    2011-12-05

    Hydrides of numerous transition metal complexes can be generated by the heterolytic cleavage of H{sub 2} gas such that they offer alternatives to using main group hydrides in the regeneration of ammonia borane, a compound that has been intensely studied for hydrogen storage applications. Previously, we reported that HRh(dmpe){sub 2}, dmpe = 1,2-bis(dimethylphosphinoethane) was capable of reducing a variety of BX{sub 3} compounds having hydride affinity (HA) greater than or equal to HA of BEt{sub 3}. This study examines the reactivity of less expensive cobalt and nickel hydride complexes, (HCo(dmpe){sub 2} and [HNi(dmpe){sub 2}]{sup +}), to form B-H bonds. The hydride donor abilities ({Delta}G{sub H{sup -}}{sup o}) of HCo(dmpe){sub 2} and [HNi(dmpe){sub 2}]{sup +} were positioned on a previously established scale in acetonitrile that is cross-referenced with calculated HAs of BX{sub 3} compounds. The collective data guided our selection of BX{sub 3} compounds to investigate and aided our analysis of factors that determine favorability of hydride transfer. HCo(dmpe){sub 2} was observed to transfer H{sup -} to BX{sub 3} compounds with X = H, OC{sub 6}F{sub 5} and SPh. The reaction with B(SPh){sub 3} is accompanied by formation of (BH{sub 3}){sub 2}-dmpe and (BH{sub 2}SPh){sub 2}-dmpe products that follow from reduction of multiple BSPh bonds and loss of a dmpe ligand from Co. Reactions between HCo(dmpe){sub 2} and B(SPh){sub 3} in the presence of triethylamine result in formation of Et{sub 3}N-BH{sub 2}SPh and Et{sub 3}N-BH{sub 3} with no loss of dmpe ligand. Reactions of the cationic complex [HNi(dmpe){sub 2}]{sup +} with B(SPh){sub 3} under analogous conditions give Et{sub 3}N-BH{sub 2}SPh as the final product along with the nickel-thiolate complex [Ni(dmpe){sub 2}(SPh)]{sup +}. The synthesis and characterization of HCo(dedpe){sub 2} (dedpe = diethyldiphenyl(phosphino)ethane) from H{sub 2} and a base is also discussed; including the formation of an uncommon trans

  15. Synthesis and Hydride Transfer Reactions of Cobalt and Nickel Hydride Complexes to BX₃ Compounds

    SciTech Connect

    Mock, Michael T.; Potter, Robert G.; O'Hagan, Molly; Camaioni, Donald M.; Dougherty, William G.; Kassel, W. Scott; DuBois, Daniel L.

    2011-10-31

    Hydrides of numerous transition metal complexes can be generated by the heterolytic cleavage of H₂ gas such that they offer alternatives to using main group hydrides in the regeneration of ammonia borane, a compound that has been intensely studied for hydrogen storage applications. Previously, we reported that HRh(dmpe)₂ (dmpe = 1,2-bis(dimethylphosphinoethane)) was capable of reducing a variety of BX₃ compounds having a hydride affinity (HA) greater than or equal to the HA of BEt₃. This study examines the reactivity of less expensive cobalt and nickel hydride complexes, HCo(dmpe)₂ and [HNi(dmpe)₂]+, to form B–H bonds. The hydride donor abilities (ΔGH °) of HCo(dmpe)₂ and [HNi(dmpe)₂]+ were positioned on a previously established scale in acetonitrile that is cross-referenced with calculated HAs of BX₃ compounds. The collective data guided our selection of BX₃ compounds to investigate and aided our analysis of factors that determine favorability of hydride transfer. HCo(dmpe)₂ was observed to transfer H to BX₃ compounds with X = H, OC₆F₅, and SPh. The reaction with B(SPh)₃ is accompanied by the formation of dmpe-(BH₃)₂ and dmpe-(BH₂(SPh))₂ products that follow from a reduction of multiple B–SPh bonds and a loss of dmpe ligands from cobalt. Reactions between HCo(dmpe)₂ and B(SPh)₃ in the presence of triethylamine result in the formation of Et₃N–BH₂SPh and Et₃N–BH₃ with no loss of a dmpe ligand. Reactions of the cationic complex [HNi(dmpe)₂]+ with B(SPh)₃ under analogous conditions give Et₃N–BH₂SPh as the final product along with the nickel–thiolate complex [Ni(dmpe)₂(SPh)]+. The synthesis and characterization of HCo(dedpe)₂ (dedpe = Et₂PCH₂CH₂PPh₂) from H₂ and a base is also discussed, including the formation of an uncommon trans dihydride species, trans-[(H)₂Co(dedpe)₂][BF₄].

  16. Synthesis and hydride transfer reactions of cobalt and nickel hydride complexes to BX3 compounds.

    PubMed

    Mock, Michael T; Potter, Robert G; O'Hagan, Molly J; Camaioni, Donald M; Dougherty, William G; Kassel, W Scott; DuBois, Daniel L

    2011-12-01

    Hydrides of numerous transition metal complexes can be generated by the heterolytic cleavage of H(2) gas such that they offer alternatives to using main group hydrides in the regeneration of ammonia borane, a compound that has been intensely studied for hydrogen storage applications. Previously, we reported that HRh(dmpe)(2) (dmpe = 1,2-bis(dimethylphosphinoethane)) was capable of reducing a variety of BX(3) compounds having a hydride affinity (HA) greater than or equal to the HA of BEt(3). This study examines the reactivity of less expensive cobalt and nickel hydride complexes, HCo(dmpe)(2) and [HNi(dmpe)(2)](+), to form B-H bonds. The hydride donor abilities (ΔG(H(-))°) of HCo(dmpe)(2) and [HNi(dmpe)(2)](+) were positioned on a previously established scale in acetonitrile that is cross-referenced with calculated HAs of BX(3) compounds. The collective data guided our selection of BX(3) compounds to investigate and aided our analysis of factors that determine favorability of hydride transfer. HCo(dmpe)(2) was observed to transfer H(-) to BX(3) compounds with X = H, OC(6)F(5), and SPh. The reaction with B(SPh)(3) is accompanied by the formation of dmpe-(BH(3))(2) and dmpe-(BH(2)(SPh))(2) products that follow from a reduction of multiple B-SPh bonds and a loss of dmpe ligands from cobalt. Reactions between HCo(dmpe)(2) and B(SPh)(3) in the presence of triethylamine result in the formation of Et(3)N-BH(2)SPh and Et(3)N-BH(3) with no loss of a dmpe ligand. Reactions of the cationic complex [HNi(dmpe)(2)](+) with B(SPh)(3) under analogous conditions give Et(3)N-BH(2)SPh as the final product along with the nickel-thiolate complex [Ni(dmpe)(2)(SPh)](+). The synthesis and characterization of HCo(dedpe)(2) (dedpe = Et(2)PCH(2)CH(2)PPh(2)) from H(2) and a base is also discussed, including the formation of an uncommon trans dihydride species, trans-[(H)(2)Co(dedpe)(2)][BF(4)]. PMID:22040085

  17. Dynamic aspects of antibody:oligosaccharide complexes characterized by molecular dynamics simulations and saturation transfer difference nuclear magnetic resonance.

    PubMed

    Theillet, François-Xavier; Frank, Martin; Vulliez-Le Normand, Brigitte; Simenel, Catherine; Hoos, Sylviane; Chaffotte, Alain; Bélot, Frédéric; Guerreiro, Catherine; Nato, Farida; Phalipon, Armelle; Mulard, Laurence A; Delepierre, Muriel

    2011-12-01

    Carbohydrates are likely to maintain significant conformational flexibility in antibody (Ab):carbohydrate complexes. As demonstrated herein for the protective monoclonal Ab (mAb) F22-4 recognizing the Shigella flexneri 2a O-antigen (O-Ag) and numerous synthetic oligosaccharide fragments thereof, the combination of molecular dynamics simulations and nuclear magnetic resonance saturation transfer difference experiments, supported by physicochemical analysis, allows us to determine the binding epitope and its various contributions to affinity without using any modified oligosaccharides. Moreover, the methods used provide insights into ligand flexibility in the complex, thus enabling a better understanding of the Ab affinities observed for a representative set of synthetic O-Ag fragments. Additionally, these complementary pieces of information give evidence to the ability of the studied mAb to recognize internal as well as terminal epitopes of its cognate polysaccharide antigen. Hence, we show that an appropriate combination of computational and experimental methods provides a basis to explore carbohydrate functional mimicry and receptor binding. The strategy may facilitate the design of either ligands or carbohydrate recognition domains, according to needed improvements of the natural carbohydrate:receptor properties. PMID:21610193

  18. Role of Constituent Hard Polymer in Enhancing Lithium Transference Number of Lithium Salt-Polymer Complexes

    NASA Astrophysics Data System (ADS)

    Jo, Gyuha; Park, Moon Jeong

    2015-03-01

    Lithium polymer batteries have been projected as promising energy storage systems, owing to their unique advantages such as long cycle life, high specific capacity, and high cell potential. While the polymer electrolytes such as poly(ethylene oxide) (PEO) employed in lithium polymer batteries have high ionic conductivity and low volatility, the PEO-lithium salt complexes indicated immense shortcomings of concentration polarization, ascribed to the motion of free anions within PEO. This has limited charge/discharge rate of lithium batteries. In this study, we present a new methodology for improving the ionic conductivity and lithium transference number of PEO, by block copolymerization with a hard polymer, namely poly(dithiooxamide) (PDTOA). Compared to a simple PEO/PDTOA blend, lithium-salt doped PEO-b-PDTOA block copolymers exhibited significantly improved ionic conductivity values. Further, lithium transference numbers as high as 0.66 were observed, which are much higher than the corresponding values for conventional PEO-salt electrolytes (~ 0 . 25).

  19. Electron transfer reactions in the alkene mono-oxygenase complex from Nocardia corallina B-276.

    PubMed Central

    Gallagher, S C; Cammack, R; Dalton, H

    1999-01-01

    Nocardia corallina B-276 possesses a multi-component enzyme, alkene mono-oxygenase (AMO), that catalyses the stereoselective epoxygenation of alkenes. The reductase component of this system has been shown by EPR and fluorescence spectroscopy to contain two prosthetic groups, an FAD centre and a [2Fe-2S] cluster. The role of these centres in the epoxygenation reaction was determined by midpoint potential measurements and electron transfer kinetics. The order of potentials of the prosthetic groups of the reductase were FAD/FAD.=-216 mV, [2Fe-2S]/[2Fe-2S].=-160 mV and FAD./FAD.=-134 mV. Combined, these data implied that the reductase component supplied the energy required for the epoxygenation reaction and allowed a prediction of the mechanism of electron transfer within the AMO complex. The FAD moiety was reduced by bound NADH in a two-electron reaction. The electrons were then transported to the [2Fe-2S] centre one at a time, which in turn reduced the di-iron centre of the epoxygenase. Reduction of the di-iron centre is required for oxygen binding and substrate oxidation. PMID:10085230

  20. Utilizing Metal to Ligand Charge Transfer States of MM Quadruply Bonded Complexes for Photovoltaic Applications

    NASA Astrophysics Data System (ADS)

    Lewis, Sharlene A.; Brown-Xu, Samantha E.; Chisholm, Malcolm H.; Epstein, Arthur J.

    2013-06-01

    In this contribution, we report two examples of our efforts to develop MM quadruply bonded complexes for photovoltaic applications. In the first example, evidence, based on femtosecond transient absorption and time resolved infrared spectroscopy, is presented for photoinduced charge transfer from the Mo_{2}δ orbital of the quadruply bonded molecule trans-Mo_{2}(TiPB)_{2}BTh)_{2}, where TiPB = 2,4,6-triisopropyl benzoate and BTh = 2,2'-bithienylcarboxylate, to di-n-octyl perylene diimide and di-n-hexylheptyl perylene diimide in thin films and solutions of the mixtures. In the second example, the structural and photophysical properties of the new compounds trans-M_{2}(TiPB)_{2}(L)_{2} and trans-M_{2}(TiPB)_{2}(L')_{2}, where M=Mo or W and L and L' are triphenylamine-cyanoacrylate ligands are presented. These ligands promote intense metal to ligand charge transfer transitions that span the range 550 to 1100 nm. The excited states have been studied by transient absorption and time resolved infrared spectroscopy

  1. Solvent influence on the thermodynamics for hydride transfer from bis(diphosphine) complexes of nickel.

    PubMed

    Connelly Robinson, Samantha J; Zall, Christopher M; Miller, Deanna L; Linehan, John C; Appel, Aaron M

    2016-06-14

    The thermodynamic hydricity of a metal hydride can vary considerably between solvents. This parameter can be used to determine the favourability of a hydride-transfer reaction, such as the reaction between a metal hydride and CO2 to produce formate. Because the hydricities of these species do not vary consistently between solvents, reactions that are thermodynamically unfavourable in one solvent can be favourable in others. The hydricity of a water-soluble, bis-phosphine nickel hydride complex was compared to the hydricity of formate in water and in acetonitrile. Formate is a better hydride donor than [HNi(dmpe)2](+) by 7 kcal mol(-1) in acetonitrile, and no hydride transfer from [HNi(dmpe)2](+) to CO2 occurs in this solvent. The hydricity of [HNi(dmpe)2](+) is greatly improved in water relative to acetonitrile, in that reduction of CO2 to formate by [HNi(dmpe)2](+) was found to be thermodynamically downhill by 8 kcal mol(-1). Catalysis for the hydrogenation of CO2 was pursued, but the regeneration of [HNi(dmpe)2] under catalytic conditions was unfavourable. However, the present results demonstrate that the solvent dependence of thermodynamic parameters such as hydricity and acidity can be exploited in order to produce systems with balanced or favourable overall thermodynamics. This approach should be advantageous for the design of future water-soluble catalysts. PMID:27071366

  2. Ionic Charge Transfer Complex Induced Visible Light Harvesting and Photocharge Generation in Perovskite.

    PubMed

    Ng, Tsz-Wai; Thachoth Chandran, Hrisheekesh; Chan, Chiu-Yee; Lo, Ming-Fai; Lee, Chun-Sing

    2015-09-16

    Organometal trihalide perovskite has recently emerged as a new class of promising material for high efficiency solar cells applications. While excess ions in perovskites are recently getting a great deal of attention, there is so far no clear understanding on both their formation and relating ions interaction to the photocharge generation in perovskite. Herein, we showed that tremendous ions indeed form during the initial stage of perovskite formation when the organic methylammonium halide (MAXa, Xa=Br and I) meets the inorganic PbXb2 (Xb=Cl, Br, I). The strong charge exchanges between the Pb2+ cations and Xa- anions result in formation of ionic charge transfer complexes (iCTC). MAXa parties induce empty valence electronic states within the forbidden bandgap of PbXb2. The strong surface dipole provide sufficient driving force for sub-bandgap electron transition with energy identical to the optical bandgap of forming perovskites. Evidences from XPS/UPS and photoluminescence studies showed that the light absorption, exciton dissociation, and photocharge generation of the perovskites are closely related to the strong ionic charge transfer interactions between Pb2+ and Xa- ions in the perovskite lattices. Our results shed light on mechanisms of light harvesting and subsequent free carrier generation in perovskites. PMID:26305717

  3. The electron transfer complex between nitrous oxide reductase and its electron donors.

    PubMed

    Dell'acqua, Simone; Moura, Isabel; Moura, José J G; Pauleta, Sofia R

    2011-12-01

    Identifying redox partners and the interaction surfaces is crucial for fully understanding electron flow in a respiratory chain. In this study, we focused on the interaction of nitrous oxide reductase (N(2)OR), which catalyzes the final step in bacterial denitrification, with its physiological electron donor, either a c-type cytochrome or a type 1 copper protein. The comparison between the interaction of N(2)OR from three different microorganisms, Pseudomonas nautica, Paracoccus denitrificans, and Achromobacter cycloclastes, with their physiological electron donors was performed through the analysis of the primary sequence alignment, electrostatic surface, and molecular docking simulations, using the bimolecular complex generation with global evaluation and ranking algorithm. The docking results were analyzed taking into account the experimental data, since the interaction is suggested to have either a hydrophobic nature, in the case of P. nautica N(2)OR, or an electrostatic nature, in the case of P. denitrificans N(2)OR and A. cycloclastes N(2)OR. A set of well-conserved residues on the N(2)OR surface were identified as being part of the electron transfer pathway from the redox partner to N(2)OR (Ala495, Asp519, Val524, His566 and Leu568 numbered according to the P. nautica N(2)OR sequence). Moreover, we built a model for Wolinella succinogenes N(2)OR, an enzyme that has an additional c-type-heme-containing domain. The structures of the N(2)OR domain and the c-type-heme-containing domain were modeled and the full-length structure was obtained by molecular docking simulation of these two domains. The orientation of the c-type-heme-containing domain relative to the N(2)OR domain is similar to that found in the other electron transfer complexes. PMID:21739254

  4. Low Light Adaptation: Energy Transfer Processes in Different Types of Light Harvesting Complexes from Rhodopseudomonas palustris

    PubMed Central

    Moulisová, Vladimíra; Luer, Larry; Hoseinkhani, Sajjad; Brotosudarmo, Tatas H.P.; Collins, Aaron M.; Lanzani, Guglielmo; Blankenship, Robert E.; Cogdell, Richard J.

    2009-01-01

    Abstract Energy transfer processes in photosynthetic light harvesting 2 (LH2) complexes isolated from purple bacterium Rhodopseudomonas palustris grown at different light intensities were studied by ground state and transient absorption spectroscopy. The decomposition of ground state absorption spectra shows contributions from B800 and B850 bacteriochlorophyll (BChl) a rings, the latter component splitting into a low energy and a high energy band in samples grown under low light (LL) conditions. A spectral analysis reveals strong inhomogeneity of the B850 excitons in the LL samples that is well reproduced by an exponential-type distribution. Transient spectra show a bleach of both the low energy and high energy bands, together with the respective blue-shifted exciton-to-biexciton transitions. The different spectral evolutions were analyzed by a global fitting procedure. Energy transfer from B800 to B850 occurs in a mono-exponential process and the rate of this process is only slightly reduced in LL compared to high light samples. In LL samples, spectral relaxation of the B850 exciton follows strongly nonexponential kinetics that can be described by a reduction of the bleach of the high energy excitonic component and a red-shift of the low energetic one. We explain these spectral changes by picosecond exciton relaxation caused by a small coupling parameter of the excitonic splitting of the BChl a molecules to the surrounding bath. The splitting of exciton energy into two excitonic bands in LL complex is most probably caused by heterogenous composition of LH2 apoproteins that gives some of the BChls in the B850 ring B820-like site energies, and causes a disorder in LH2 structure. PMID:19948132

  5. Nonlinear Ultrafast Spectroscopy of Electron and Energy Transfer in Molecule Complexes

    SciTech Connect

    Mukamel, Shaul

    2006-02-09

    The proposed research program will focus on the development of a unified dynamical theoretical framework for calculating the optical response of molecular assemblies and applying it towards studying the interplay of energy and charge transfer in artificial chromophore-aggregate complexes. Applications will be made to poly (p phenylene vinylene), (PPV) oligomers, several families of stilbenoid aggregates with stacking through a cyclophane group, coupled porphyrin arrays, and energy funneling in phenylacetylene dendrimers. The approach is based on formulating the problem using the density- matrix and developing Liouville-space techniques which provide physical insight and are particularly suitable for computing both coherent and incoherent transport. A physical picture based on collective electronic normal modes which represent the dynamics of the optically-driven reduced single electron density matrix will be established. Femtosecond signals and optical properties will be directly related to the motions of electron-hole pairs in real space, completely avoiding the calculation of many-electron excited-state wavefunctions, thus, considerably reducing computational effort. Vibrational and solvent effects will be incorporated. Guidelines for the synthesis of new donor/bridge/acceptor molecules with desired properties such as carrier transport, optical response time scales and fluorescence quantum yields will be developed. The analogy with Thz emission spectroscopy which probes charge carrier dynamic is in semiconductor superlattices will be explored. A systematic procedure for identifying the electronic coherence sizes which control the transport and optical properties will be developed. Localization of electronic transition density matrices of large molecules will be used to break the description of their optical response into coupled chromophores. The proposal is divided into four parts: (i) Collective-Oscillator Representation of Electronic Excitations in Molecular

  6. An information theory analysis of visual complexity and dissimilarity.

    PubMed

    Donderi, Don C

    2006-01-01

    The subjective complexity of a computer-generated bitmap image can be measured by magnitude estimation scaling, and its objective complexity can be measured by its compressed file size. There is a high correlation between these measures of subjective and objective complexity over a large set of marine electronic chart and radar images. The subjective dissimilarity of a pair of bitmap images can be predicted from subjective and objective measures of the complexity of each image, and from the subjective and objective complexity of the image produced by overlaying the two simple images. In addition, the subjective complexity of the image produced by overlaying two simple images can be predicted from the subjective complexity of the simple images and the subjective dissimilarity of the image pair. The results of the experiments that generated these complexity and dissimilarity judgments are consistent with a theory, outlined here, that treats objective and subjective measures of image complexity and dissimilarity as vectors in Euclidean space. PMID:16836047

  7. Probing energy transfer events in the light harvesting complex 2 (LH2) of Rhodobacter sphaeroides with two-dimensional spectroscopy

    PubMed Central

    Fidler, Andrew F.; Singh, Ved P.; Long, Phillip D.; Dahlberg, Peter D.; Engel, Gregory S.

    2013-01-01

    Excitation energy transfer events in the photosynthetic light harvesting complex 2 (LH2) of Rhodobacter sphaeroides are investigated with polarization controlled two-dimensional electronic spectroscopy. A spectrally broadened pulse allows simultaneous measurement of the energy transfer within and between the two absorption bands at 800 nm and 850 nm. The phased all-parallel polarization two-dimensional spectra resolve the initial events of energy transfer by separating the intra-band and inter-band relaxation processes across the two-dimensional map. The internal dynamics of the 800 nm region of the spectra are resolved as a cross peak that grows in on an ultrafast time scale, reflecting energy transfer between higher lying excitations of the B850 chromophores into the B800 states. We utilize a polarization sequence designed to highlight the initial excited state dynamics which uncovers an ultrafast transfer component between the two bands that was not observed in the all-parallel polarization data. We attribute the ultrafast transfer component to energy transfer from higher energy exciton states to lower energy states of the strongly coupled B850 chromophores. Connecting the spectroscopic signature to the molecular structure, we reveal multiple relaxation pathways including a cyclic transfer of energy between the two rings of the complex. PMID:24160544

  8. Probing energy transfer events in the light harvesting complex 2 (LH2) of Rhodobacter sphaeroides with two-dimensional spectroscopy

    SciTech Connect

    Fidler, Andrew F.; Singh, Ved P.; Engel, Gregory S.; Long, Phillip D.; Dahlberg, Peter D.

    2013-10-21

    Excitation energy transfer events in the photosynthetic light harvesting complex 2 (LH2) of Rhodobacter sphaeroides are investigated with polarization controlled two-dimensional electronic spectroscopy. A spectrally broadened pulse allows simultaneous measurement of the energy transfer within and between the two absorption bands at 800 nm and 850 nm. The phased all-parallel polarization two-dimensional spectra resolve the initial events of energy transfer by separating the intra-band and inter-band relaxation processes across the two-dimensional map. The internal dynamics of the 800 nm region of the spectra are resolved as a cross peak that grows in on an ultrafast time scale, reflecting energy transfer between higher lying excitations of the B850 chromophores into the B800 states. We utilize a polarization sequence designed to highlight the initial excited state dynamics which uncovers an ultrafast transfer component between the two bands that was not observed in the all-parallel polarization data. We attribute the ultrafast transfer component to energy transfer from higher energy exciton states to lower energy states of the strongly coupled B850 chromophores. Connecting the spectroscopic signature to the molecular structure, we reveal multiple relaxation pathways including a cyclic transfer of energy between the two rings of the complex.

  9. Quantifying Information Flow between Two Chaotic Semiconductor Lasers Using Symbolic Transfer Entropy

    NASA Astrophysics Data System (ADS)

    Li, Nian-Qiang; Pan, Wei; Yan, Lian-Shan; Luo, Bin; Xu, Ming-Feng; Tang, Yi-Long

    2012-03-01

    Symbolic transfer entropy (STE) is employed to quantify the dominant direction of information flow between two chaotic-semiconductor-laser time series. The information flow in unidirectionally and bidirectionally coupled systems was analyzed systematically. Numerical results show that the dependence relationship can be revealed if there exists any coupling between two chaotic semiconductor lasers. More importantly, in both unsynchronized and good synchronization regimes, the STE can be used to quantify the direction of information flow between the lasers, although the former case leads to a better identification. The results thus establish STE as an effective tool for quantifying the direction of information flow between chaotic-laser-based systems.

  10. Information Transfer and Cognitive Mismatch: A Popperian Model for Studies of Public Understanding.

    ERIC Educational Resources Information Center

    Abbott, R.

    1997-01-01

    The deficiencies and distortions revealed in studies of public understanding of science, intuitive physics, nutritional myths and misunderstandings, and mental mapping of geographical space are defects in information transfer from the physical and intellectual realms to the subjective realms of individuals (Popper's three "Worlds"). Argues that…

  11. Information Transfer Problems of the Partially Sighted: Recent Results and Project Summary.

    ERIC Educational Resources Information Center

    Genensky, S. M.; And Others

    The fourth in a series of Rand reports on information transfer problems of the partially sighted reviews earlier reports and describes an experimental secretarial closed circuit TV (CCTV) system which enables the partially sighted to type from a printed or handwritten manuscript. Discussed are experiments using a pseudocolor system to determine…

  12. 77 FR 3487 - Agency Information Collection Activities: Transfer of Cargo to a Container Station

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-01-24

    ... a Container Station AGENCY: U.S. Customs and Border Protection (CBP), Department of Homeland... concerning Transfer of Cargo to a Container Station. This request for comment is being made pursuant to the... keepers from the collection of information (total capital/startup costs and operations and...

  13. 75 FR 26268 - Agency Information Collection Activities: Permit To Transfer Containers to a Container Station

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-05-11

    ... Containers to a Container Station AGENCY: U.S. Customs and Border Protection, Department of Homeland Security... concerning the: Permit to Transfer Containers to a Container Station. This request for comment is being made... keepers from the collection of information (a total capital/startup costs and operations and...

  14. A REVIEW OF EFFORTS TO ORGANIZE INFORMATION ABOUT HUMAN LEARNING, TRANSFER, AND RETENTION.

    ERIC Educational Resources Information Center

    GINSBERG, ROSE; AND OTHERS

    FOURTEEN EFFORTS TO ORGANIZE AVAILABLE INFORMATION ON HUMAN LEARNING, TRANSFER, AND RETENTION ARE SUMMARIZED AND EVALUATED ON SIX CRITERIA--BEHAVIORAL SIGNIFICANCE OF CATEGORIES, SCOPE, OBJECTIVITY AND RELIABILITY OF CATEGORIES, PROGNOSIS FOR THE SYSTEM, LOGICAL STRUCTURE, AND HEURISTIC VALUE OF THE SYSTEM. ATTENTION IS GIVEN TO OTHER SOURCES OF…

  15. The Concept of "National Security" and Its Effect on Information Transfer

    ERIC Educational Resources Information Center

    Klempner, I. M.

    1973-01-01

    Examined is the evolving definition and interpretation of national security as it is applied to the control of security-classified documents and as manifested by Federal employee attitudes toward dissemination of nonsecurity classified documents. The role of the special librarian or information scientist in the transfer process is also examined.…

  16. Efficient transfer of information from hexitol nucleic acids to RNA during nonenzymatic oligomerization

    NASA Technical Reports Server (NTRS)

    Kozlov, I. A.; De Bouvere, B.; Van Aerschot, A.; Herdewijn, P.; Orgel, L. E.

    1999-01-01

    Hexitol nucleic acids (HNAs) are DNA analogues that contain the standard nucleoside bases attached to a phosphorylated 1,5-anhydrohexitol backbone. We find that HNAs support efficient information transfer in nonensymatic template-directed reactions. HNA heterosequences appeared to be superior to the corresponding DNA heterosequences in facilitating synthesis of complementary oligonucleotides from nucleoside-5'-phosphoro-2-methyl imidazolides.

  17. 48 CFR 52.232-38 - Submission of Electronic Funds Transfer Information with Offer.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... information that is required to make payment by electronic funds transfer (EFT) under any contract that... 48 Federal Acquisition Regulations System 2 2010-10-01 2010-10-01 false Submission of Electronic... System FEDERAL ACQUISITION REGULATION (CONTINUED) CLAUSES AND FORMS SOLICITATION PROVISIONS AND...

  18. Thermodynamic cost of computation, algorithmic complexity and the information metric

    NASA Technical Reports Server (NTRS)

    Zurek, W. H.

    1989-01-01

    Algorithmic complexity is discussed as a computational counterpart to the second law of thermodynamics. It is shown that algorithmic complexity, which is a measure of randomness, sets limits on the thermodynamic cost of computations and casts a new light on the limitations of Maxwell's demon. Algorithmic complexity can also be used to define distance between binary strings.

  19. GAM-HEAT: A computer code to compute heat transfer in complex enclosures

    SciTech Connect

    Cooper, R.E.; Taylor, J.R.

    1992-12-01

    This report discusses the GAM[underscore]HEAT code which was developed for heat transfer analyses associated with postulated Double Ended Guilliotine Break Loss Of Coolant Accidents (DEGB LOCA) resulting in a drained reactor vessel. In these analyses the gamma radiation resulting from fission product decay constitutes the primary source of energy as a function of time. This energy is deposited into the various reactor components and is re-radiated as thermal energy. The code accounts for all radiant heat exchanges within and leaving the reactor enclosure. The SRS reactors constitute complex radiant exchange enclosures since there are many assemblies of various types within the primary enclosure and most of the assemblies themselves constitute enclosures. GAM-HEAT accounts for this complexity by processing externally generated view factors and connectivity matrices as discussed below, and also accounts for convective, conductive, and advective heat exchanges. The code is structured such that it is applicable for many situations involving heat exchange between surfaces within a radiatively passive medium.

  20. GAM-HEAT: A computer code to compute heat transfer in complex enclosures. Revision 2

    SciTech Connect

    Cooper, R.E.; Taylor, J.R.

    1992-12-01

    This report discusses the GAM{underscore}HEAT code which was developed for heat transfer analyses associated with postulated Double Ended Guilliotine Break Loss Of Coolant Accidents (DEGB LOCA) resulting in a drained reactor vessel. In these analyses the gamma radiation resulting from fission product decay constitutes the primary source of energy as a function of time. This energy is deposited into the various reactor components and is re-radiated as thermal energy. The code accounts for all radiant heat exchanges within and leaving the reactor enclosure. The SRS reactors constitute complex radiant exchange enclosures since there are many assemblies of various types within the primary enclosure and most of the assemblies themselves constitute enclosures. GAM-HEAT accounts for this complexity by processing externally generated view factors and connectivity matrices as discussed below, and also accounts for convective, conductive, and advective heat exchanges. The code is structured such that it is applicable for many situations involving heat exchange between surfaces within a radiatively passive medium.

  1. Exciton Transfer and Emergent Excitonic States in Oppositely-Charged Conjugated Polyelectrolyte Complexes.

    PubMed

    Hollingsworth, William R; Segura, Carmen; Balderrama, Jonathan; Lopez, Nathaniel; Schleissner, Pamela; Ayzner, Alexander L

    2016-08-11

    Photosynthetic organisms have mastered the use of "soft" macromolecular assemblies for light absorption and concentration of electronic excitation energy. Nature's design centers on an optically inactive protein-based backbone that acts as a host matrix for an array of light-harvesting pigment molecules. The pigments are organized in space such that excited states can migrate between molecules, ultimately delivering the energy to the reaction center. Here we report our investigation of an artificial light-harvesting energy transfer antenna based on complexes of oppositely charged conjugated polyelectrolytes (CPEs). The conjugated backbone and the charged side chains of the CPE lead to an architecture that simultaneously functions as a structural scaffold and an electronic energy "highway". We find that the process of ionic complex formation leads to a remarkable change in the excitonic wavefunction of the energy acceptor, which manifests in a dramatic increase in the fluorescence quantum yield. We argue that the extended backbone of the donor CPE effectively templates a planarized acceptor polymer, leading to excited states that are highly delocalized along the polymer backbone. PMID:27428604

  2. Effect of oxygen transfer rate on the composition of the pectolytic enzyme complex of Aspergillus niger

    SciTech Connect

    Zetelaki-Horvath, K.; Vas, K.

    1981-01-01

    Optimal agitation and aeration conditions (assuring O/sub 2/ transfer rates (OTR) of 12-179 mmol/L-h) were determined for pectin lyase (PL) synthesis of an Aspergillus niger strain. Components of the pectolytic enzyme complex were also investigated in order to determine whether their O/sub 2/ demand is identical with or different from that of pectin lyase. Should the latter be the case, a possibility would be given to produce enzyme complexes of different agitation and aeration conditions. The mycelium yield of Aspergillus niger was maximum at an OTR of 100 mmol/L-h. The yields of the various pectolytic enzymes reached maximum at different OTRs. PL production was highest (0.555 mumol/min-mL) at an OTR of 60 mmol/L-h. Endopolygalacturonase (PG) production has a maximum at OTR 49 mmol/L-h, with a 2nd peak at 100-135 mmol O2/L-h. Pectin esterase (PE) synthesis showed a maximum at an OTR of 12-14 mmol/L-h, while both apple juice clarifying and macerating activities gave 2 maximum at 14 and 60 mmol/L-h due to the optima of PE and endo-PG. Macerating activity showed a high value at OTR optimal for PL production as well.

  3. GAM-HEAT: A computer code to compute heat transfer in complex enclosures

    NASA Astrophysics Data System (ADS)

    Cooper, R. E.; Taylor, J. R.

    1992-12-01

    This report discusses the GAM-HEAT code which was developed for heat transfer analyses associated with postulated Double Ended Guillotine Break Loss Of Coolant Accidents (DEGB LOCA) resulting in a drained reactor vessel. In these analyses the gamma radiation resulting from fission product decay constitutes the primary source of energy as a function of time. This energy is deposited into the various reactor components and is re-radiated as thermal energy. The code accounts for all radiant heat exchanges within and leaving the reactor enclosure. The SRS reactors constitute complex radiant exchange enclosures since there are many assemblies of various types within the primary enclosure and most of the assemblies themselves constitute enclosures. GAM-HEAT accounts for this complexity by processing externally generated view factors and connectivity matrices as discussed below, and also accounts for convective, conductive, and advective heat exchanges. The code is structured such that it is applicable for many situations involving heat exchange between surfaces within a radiatively passive medium.

  4. Fluorescence resonance energy transfer analysis of escherichia coli RNA polymerase and polymerase-DNA complexes.

    PubMed

    Heyduk, T; Niedziela-Majka, A

    Fluorescence resonance energy transfer (FRET) is a technique allowing measurements of atomic-scale distances in diluted solutions of macromolecules under native conditions. This feature makes FRET a powerful tool to study complicated biological assemblies. In this report we review the applications of FRET to studies of transcription initiation by Escherichia coli RNA polymerase. The versatility of FRET for studies of a large macromolecular assembly such as RNA polymerase is illustrated by examples of using FRET to address several different aspects of transcription initiation by polymerase. FRET has been used to determine the architecture of polymerase, its complex with single-stranded DNA, and the conformation of promoter fragment bound to polymerase. FRET has been also used as a binding assay to determine the thermodynamics of promoter DNA fragment binding to the polymerase. Functional conformational changes in the specificity subunit of polymerase responsible for the modulation of the promoter binding activity of the enzyme and the mechanistic aspects of the transition from the initiation to the elongation complex were also investigated. PMID:11987181

  5. Single-molecule interfacial electron transfer in donor-bridge-nanoparticle acceptor complexes.

    PubMed

    Jin, Shengye; Snoeberger, Robert C; Issac, Abey; Stockwell, David; Batista, Victor S; Lian, Tianquan

    2010-11-18

    Photoinduced interfacial electron transfer (IET) in sulforhodamine B (SRhB)-aminosilane-Tin oxide (SnO(2)) nanoparticle donor-bridge-acceptor complexes has been studied on a single molecule and ensemble average level. On both SnO(2) and ZrO(2), the sum of single molecule fluorescence decays agree with the ensemble average results, suggesting complete sampling of molecules under single molecule conditions. Shorter fluorescence lifetime on SnO(2) than on ZrO(2) is observed and attributed to IET from SRhB to SnO(2). Single molecule lifetimes fluctuate with time and vary among different molecules, suggesting both static and dynamic IET heterogeneity in this system. Computational modeling of the complexes shows a distribution of molecular conformation, leading to a distribution of electronic coupling strengths and ET rates. It is likely that the conversion between these conformations led to the fluctuation of ET rate and fluorescence lifetime on the single molecule level. PMID:20225886

  6. Rotordynamic analysis using the Complex Transfer Matrix: An application to elastomer supports using the viscoelastic correspondence principle

    NASA Astrophysics Data System (ADS)

    Varney, Philip; Green, Itzhak

    2014-11-01

    Numerous methods are available to calculate rotordynamic whirl frequencies, including analytic methods, finite element analysis, and the transfer matrix method. The typical real-valued transfer matrix (RTM) suffers from several deficiencies, including lengthy computation times and the inability to distinguish forward and backward whirl. Though application of complex coordinates in rotordynamic analysis is not novel per se, specific advantages gained from using such coordinates in a transfer matrix analysis have yet to be elucidated. The present work employs a complex coordinate redefinition of the transfer matrix to obtain reduced forms of the elemental transfer matrices in inertial and rotating reference frames, including external stiffness and damping. Application of the complex-valued state variable redefinition results in a reduction of the 8×8 RTM to the 4×4 Complex Transfer Matrix (CTM). The CTM is advantageous in that it intrinsically separates forward and backward whirl, eases symbolic manipulation by halving the transfer matrices’ dimension, and provides significant improvement in computation time. A symbolic analysis is performed on a simple overhung rotor to demonstrate the mathematical motivation for whirl frequency separation. The CTM's utility is further shown by analyzing a rotordynamic system supported by viscoelastic elastomer rings. Viscoelastic elastomer ring supports can provide significant damping while reducing the cost and complexity associated with conventional components such as squeeze film dampers. The stiffness and damping of a viscoelastic damper ring are determined herein as a function of whirl frequency using the viscoelastic correspondence principle and a constitutive fractional calculus viscoelasticity model. The CTM is then employed to obtain the characteristic equation, where the whirl frequency dependent stiffness and damping of the elastomer supports are included. The Campbell diagram is shown, demonstrating the CTM

  7. Validated spectrophotometric methods for determination of sodium valproate based on charge transfer complexation reactions

    NASA Astrophysics Data System (ADS)

    Belal, Tarek S.; El-Kafrawy, Dina S.; Mahrous, Mohamed S.; Abdel-Khalek, Magdi M.; Abo-Gharam, Amira H.

    2016-02-01

    This work presents the development, validation and application of four simple and direct spectrophotometric methods for determination of sodium valproate (VP) through charge transfer complexation reactions. The first method is based on the reaction of the drug with p-chloranilic acid (p-CA) in acetone to give a purple colored product with maximum absorbance at 524 nm. The second method depends on the reaction of VP with dichlone (DC) in dimethylformamide forming a reddish orange product measured at 490 nm. The third method is based upon the interaction of VP and picric acid (PA) in chloroform resulting in the formation of a yellow complex measured at 415 nm. The fourth method involves the formation of a yellow complex peaking at 361 nm upon the reaction of the drug with iodine in chloroform. Experimental conditions affecting the color development were studied and optimized. Stoichiometry of the reactions was determined. The proposed spectrophotometric procedures were effectively validated with respect to linearity, ranges, precision, accuracy, specificity, robustness, detection and quantification limits. Calibration curves of the formed color products with p-CA, DC, PA and iodine showed good linear relationships over the concentration ranges 24-144, 40-200, 2-20 and 1-8 μg/mL respectively. The proposed methods were successfully applied to the assay of sodium valproate in tablets and oral solution dosage forms with good accuracy and precision. Assay results were statistically compared to a reference pharmacopoeial HPLC method where no significant differences were observed between the proposed methods and reference method.

  8. Validated spectrophotometric methods for determination of sodium valproate based on charge transfer complexation reactions.

    PubMed

    Belal, Tarek S; El-Kafrawy, Dina S; Mahrous, Mohamed S; Abdel-Khalek, Magdi M; Abo-Gharam, Amira H

    2016-02-15

    This work presents the development, validation and application of four simple and direct spectrophotometric methods for determination of sodium valproate (VP) through charge transfer complexation reactions. The first method is based on the reaction of the drug with p-chloranilic acid (p-CA) in acetone to give a purple colored product with maximum absorbance at 524nm. The second method depends on the reaction of VP with dichlone (DC) in dimethylformamide forming a reddish orange product measured at 490nm. The third method is based upon the interaction of VP and picric acid (PA) in chloroform resulting in the formation of a yellow complex measured at 415nm. The fourth method involves the formation of a yellow complex peaking at 361nm upon the reaction of the drug with iodine in chloroform. Experimental conditions affecting the color development were studied and optimized. Stoichiometry of the reactions was determined. The proposed spectrophotometric procedures were effectively validated with respect to linearity, ranges, precision, accuracy, specificity, robustness, detection and quantification limits. Calibration curves of the formed color products with p-CA, DC, PA and iodine showed good linear relationships over the concentration ranges 24-144, 40-200, 2-20 and 1-8μg/mL respectively. The proposed methods were successfully applied to the assay of sodium valproate in tablets and oral solution dosage forms with good accuracy and precision. Assay results were statistically compared to a reference pharmacopoeial HPLC method where no significant differences were observed between the proposed methods and reference method. PMID:26574649

  9. Bonding and charge transfer in nitrogen-donor uranyl complexes: insights from NEXAFS spectra.

    PubMed

    Pemmaraju, C D; Copping, Roy; Wang, Shuao; Janousch, Markus; Teat, Simon J; Tyliszcak, Tolek; Canning, Andrew; Shuh, David K; Prendergast, David

    2014-11-01

    We investigate the electronic structure of three newly synthesized nitrogen-donor uranyl complexes [(UO2)(H2bbp)Cl2], [(UO)2(Hbbp)(Py)Cl], and [(UO2)(bbp)(Py)2] using a combination of near-edge X-ray absorption fine structure (NEXAFS) spectroscopy experiments and simulations. The complexes studied feature derivatives of the tunable tridentate N-donor ligand 2,6-bis(2-benzimidazyl)pyridine (bbp) and exhibit discrete chemical differences in uranyl coordination. The sensitivity of the N K-edge X-ray absorption spectrum to local bonding and charge transfer is exploited to systematically investigate the evolution of structural as well as electronic properties across the three complexes. A thorough interpretation of the measured experimental spectra is achieved via ab initio NEXAFS simulations based on the eXcited electron and Core-Hole (XCH) approach and enables the assignment of spectral features to electronic transitions on specific absorbing sites. We find that ligand-uranyl bonding leads to a signature blue shift in the N K-edge absorption onset, resulting from charge displacement toward the uranyl, while changes in the equatorial coordination shell of the uranyl lead to more subtle modulations in the spectral features. Theoretical simulations show that the flexible local chemistry at the nonbinding imidazole-N sites of the bbp ligand is also reflected in the NEXAFS spectra and highlights potential synthesis strategies to improve selectivity. In particular, we find that interactions of the bbp ligand with solvent molecules can lead to changes in ligand-uranyl binding geometry while also modulating the K-edge absorption. Our results suggest that NEXAFS spectroscopy combined with first-principles interpretation can offer insights into the coordination chemistry of analogous functionalized conjugated ligands. PMID:25330350

  10. Triplet exciton energy transfer in polyfluorene doped with heavy metal complexes studied using photoluminescence and photoinduced absorption

    NASA Astrophysics Data System (ADS)

    Liao, H. H.; Meng, H. F.; Horng, S. F.; Lee, W. S.; Yang, J. M.; Liu, C. C.; Shy, J. T.; Chen, F. C.; Hsu, C. S.

    2006-12-01

    Modulated photoinduced absorption and photoluminescence are used to study triplet-to-triplet Dexter energy transfer in Ir-complexes/polyfluorene blend systems. There is no Dexter energy transfer for red iridium (III)bis[2-(9,9-dibutylfluorenyl)-1-isoquinoline(acetylacetonate)] (DFIr) and red iridium (III) bis([2-(2-benzo-thienyl)pyridinatoN,C3] acetyl-acetonate) (BtpIr) dopants. Although green iridium(III)tris[2-(4-tolyl)pyridinato-N,C2] [Ir(mppy)3] has no triplet confinement in polyfluorene host, it has clear evidence for Dexter energy transfer. Aggregation and dopant lifetime are shown to significantly affect the energy transfer. The presence of Dexter transfer implies the possibility to harvest triplet excitons of polyfluorene in polymer light-emitting diodes even without carrier trapping and triplet exciton confinement.

  11. Information transfer fidelity in spin networks and ring-based quantum routers

    NASA Astrophysics Data System (ADS)

    Jonckheere, E.; Langbein, F. C.; Schirmer, S. G.

    2015-12-01

    Spin networks are endowed with an information transfer fidelity (ITF), which defines an absolute upper bound on the probability of transmission of an excitation from one spin to another. The ITF is easily computable, but the bound can be reached asymptotically in time only under certain conditions. General conditions for attainability of the bound are established, and the process of achieving the maximum transfer probability is given a dynamical model, the translation on the torus. The time to reach the maximum probability is estimated using the simultaneous Diophantine approximation, implemented using a variant of the Lenstra-Lenstra-Lovász (LLL) algorithm. For a ring with uniform couplings, the network can be made into a metric space by defining a distance (satisfying the triangle inequality) that quantifies the lack of transmission fidelity between two nodes. It is shown that transfer fidelities and transfer times can be improved significantly by means of simple controls taking the form of nondynamic, spatially localized bias fields, opening up the possibility for intelligent design of spin networks and dynamic routing of information encoded in them, while being more flexible than engineering fixed couplings to favor some transfers, and less demanding than control schemes requiring fast dynamic controls.

  12. Kinetics of mediated electron transfer between viologen groups in a self-assembled monolayer and metal complexes in solution

    NASA Astrophysics Data System (ADS)

    Schneider, Thomas; Hiley, Shauna; Buttry, Daniel A.

    1993-05-01

    Self-assembled monolayers are used in an experimental configuration which allows the extraction of the cross reaction electron exchange rate constant for the electron transfer between a viologen group embedded within the SAM and a metal complex in solution. This cross reaction rate constant is compared with predictions from the Marcus theory using the cross reaction relation and the known self-exchange rate constants for the two reagents. The results reveal that the intrinsic barrier to the electron transfer is relatively unchanged in the SAM, while the rate constant is somewhat depressed due to the long distance over which the electron must transfer.

  13. Information Transfer in the Illinois Swine Industry: How Producers Are Informed of New Technologies.

    ERIC Educational Resources Information Center

    Brashear, Genefer L.; Hollis, Gilbert; Wheeler, Matthew B.

    2000-01-01

    A survey of 127 (of 300) Illinois swine producers found that 114 owned computers; the majority used industry magazines as sources of information about new technologies; extension newsletters were used much less by corporate farm enterprises; very small numbers used electronic mail; only about half used university specialists for information; and…

  14. From School to Work and from Work to School: Information Environments and Transferring Information Literacy Practices

    ERIC Educational Resources Information Center

    Herring, James E.

    2011-01-01

    Introduction: This study, based in a Scottish secondary school, aimed to examine the views of students who were completing work experience, on their information literacy practices, and the differences they found between the school and workplace information environments while on work experience. The views of guidance teachers were also explored.…

  15. A population of glomerular glutamatergic neurons controls sensory information transfer in the mouse olfactory bulb

    PubMed Central

    Tatti, Roberta; Seal, Rebecca P.; Edwards, Robert H.; Rodriguez, Ivan; Carleton, Alan

    2014-01-01

    In sensory systems, peripheral organs convey sensory inputs to relay networks where information is shaped by local microcircuits before being transmitted to cortical areas. In the olfactory system, odorants evoke specific patterns of sensory neuron activity which are transmitted to output neurons in olfactory bulb glomeruli. How sensory information is transferred and shaped at this level remains still unclear. Here we employ mouse genetics, 2-photon microscopy, electrophysiology and optogenetics, to identify a novel population of glutamatergic neurons (VGLUT3+) in the glomerular layer of the adult mouse olfactory bulb as well as several of their synaptic targets. Both peripheral and serotoninergic inputs control VGLUT3+ neurons firing. Furthermore, we show that VGLUT3+ neurons photostimulation in vivo strongly suppresses both spontaneous and odor-evoked firing of bulbar output neurons. In conclusion, we identify and characterize here a microcircuit controlling the transfer of sensory information at an early stage of the olfactory pathway. PMID:24804702

  16. NASA technology transfer network communications and information system: TUNS user survey

    NASA Technical Reports Server (NTRS)

    1992-01-01

    Applied Expertise surveyed the users of the deployed Technology Utilization Network System (TUNS) and surveyed prospective new users in order to gather background information for developing the Concept Document of the system that will upgrade and replace TUNS. Survey participants broadly agree that automated mechanisms for acquiring, managing, and disseminating new technology and spinoff benefits information can and should play an important role in meeting NASA technology utilization goals. However, TUNS does not meet this need for most users. The survey describes a number of systematic improvements that will make it easier to use the technology transfer mechanism, and thus expedite the collection and dissemination of technology information. The survey identified 26 suggestions for enhancing the technology transfer system and related processes.

  17. Transfer entropy in magnetoencephalographic data: quantifying information flow in cortical and cerebellar networks.

    PubMed

    Wibral, Michael; Rahm, Benjamin; Rieder, Maria; Lindner, Michael; Vicente, Raul; Kaiser, Jochen

    2011-03-01

    The analysis of cortical and subcortical networks requires the identification of their nodes, and of the topology and dynamics of their interactions. Exploratory tools for the identification of nodes are available, e.g. magnetoencephalography (MEG) in combination with beamformer source analysis. Competing network topologies and interaction models can be investigated using dynamic causal modelling. However, we lack a method for the exploratory investigation of network topologies to choose from the very large number of possible network graphs. Ideally, this method should not require a pre-specified model of the interaction. Transfer entropy--an information theoretic implementation of Wiener-type causality--is a method for the investigation of causal interactions (or information flow) that is independent of a pre-specified interaction model. We analysed MEG data from an auditory short-term memory experiment to assess whether the reconfiguration of networks implied in this task can be detected using transfer entropy. Transfer entropy analysis of MEG source-level signals detected changes in the network between the different task types. These changes prominently involved the left temporal pole and cerebellum--structures that have previously been implied in auditory short-term or working memory. Thus, the analysis of information flow with transfer entropy at the source-level may be used to derive hypotheses for further model-based testing. PMID:21115029

  18. Quantum dots arrangement and energy transfer control via charge-transfer complex achieved on poly(phenylene ethynylene)/schizophyllan nanowires.

    PubMed

    Shiraki, Tomohiro; Haraguchi, Shuichi; Tsuchiya, Youichi; Shinkai, Seiji

    2009-09-01

    Assemblies of organic and inorganic compounds in the nanoscale region have contributed to the development of novel functional materials toward future applications, including sensors and opto-electronics. We succeed in fabricating hybrid nanowires composed of a conjugated polymer and semiconductor quantum dots (QDs) by a supramolecular assembly technique. The 1-D fashion of the nanowire structure is obtained by the polymer wrapping of cationic poly(phenylene ethynylene) (PPE) with helix-forming polysaccharide schizophyllan (SPG). The electrostatic interaction between cationic PPE and anionic QDs affords the nanowires decorated with QDs. Upon addition of an acceptor molecule, tetranitrofluorenone (TNF), the charge-transfer (CT) complex between PPE and TNF is formed, resulting in energy transfer from the QDs to PPE arising from the induced spectral overlap. Furthermore, the employment of the conjugated polymer allows highly sensitive quenching of the QD's emission by raising the transmission efficiency to the CT complexed electron deficient sites along the polymer backbone. PMID:19629958

  19. Energy transfer ultraviolet photodetector with 8-hydroxyquinoline derivative-metal complexes as acceptors

    NASA Astrophysics Data System (ADS)

    Wu, Shuang-Hong; Li, Wen-Lian; Chen, Zhi; Li, Shi-Bin; Wang, Xiao-Hui; Wei, Xiong-Bang

    2015-02-01

    We choose 8-hydroxyquinoline derivative-metal complexes (Beq, Mgq, and Znq) as the acceptors (A) and 4,4',4”-tri-(2-methylphenyl phenylamino) triphenylaine (m-MTDATA) as the donor (D) respectively to study the existing energy transfer process in the organic ultraviolet (UV) photodetector (PD), which has an important influence on the sensitivity of PDs. The energy transfer process from D to A without exciplex formation is discussed, differing from the working mechanism of previous PDs with Gaq [Zisheng Su, Wenlian Li, Bei Chu, Tianle Li, Jianzhuo Zhu, Guang Zhang, Fei Yan, Xiao Li, Yiren Chen and Chun-Sing Lee 2008 Appl. Phys. Lett. 93 103309)] and REq [J. B. Wang, W. L. Li, B. Chu, L. L. Chen, G. Zhang, Z. S. Su, Y. R. Chen, D. F. Yang, J. Z. Zhu, S. H. Wu, F. Yan, H. H. Liu, C. S. Lee 2010 Org. Electron. 11 1301] used as an A material. Under 365-nm UV irradiation with an intensity of 1.2 mW/cm2, the m-MTDATA:Beq blend device with a weight ratio of 1:1 shows a response of 192 mA/W with a detectivity of 6.5× 1011 Jones, which exceeds those of PDs based on Mgq (146 mA/W) and Znq (182 mA/W) due to better energy level alignment between m-MTDATA/Beq and lower radiative decay. More photophysics processes of the PDs involved are discussed in detail. Project supported by the National Natural Science Foundation of China (Grant Nos. 61371046, 61405026, 61474016, and 61421002) and China Postdoctoral Science Foundation (Grant No. 2014M552330).

  20. Synthesis and spectrophotometric studies of charge transfer complexes of p-nitroaniline with benzoic acid in different polar solvents

    NASA Astrophysics Data System (ADS)

    Singh, Neeti; Ahmad, Afaq

    2014-09-01

    The charge transfer complexes of the donor p-nitroaniline (PNA) with the π-acceptor benzoic acid (BEA) have been studied spectrophotometrically in various solvents such as acetone, ethanol, and methanol at room temperature using an absorption spectrophotometer. The outcome suggests that the formation of the CT-complex is comparatively high in less polar solvent. The stoichiometry of the CT-complex was found to be 1:1. The physical parameters of the CT-complex were evaluated by the Benesi-Hildebrand equation. The data are discussed in terms of the formation constant (KCT), molar extinction coefficient (ɛCT), Standard Gibbs free energy (ΔG0), oscillator strength (f), transition dipole moment (μEN), resonance energy (RN) and ionization potential (ID). The formation constant (KCT) of the complex was depends upon the nature of electron acceptor, donor, and polarity of solvents used. It is also observed that a charge transfer molecular complex is stabilized by hydrogen bonding. The formation of the complex has been confirmed by UV-visible, FT-IR, 1H NMR and TGA/DTA. The structure of the CT-complex is [(PNA)+ (BEA)-]. A general mechanism for its formation of the complex has also been proposed.

  1. UV-vis, IR spectra and thermal studies of charge transfer complex formed between poly(amidoamine) dendrimers and iodine.

    PubMed

    Refat, Moamen S; El-Didamony, Akram M; Grabchev, Ivo

    2007-05-01

    The intermolecular charge-transfer (CT) complexes formed between two poly(amidoamine) dendrimers (PAMAM) from zero (D1) and second generation (D2) as donor and iodine as sigma-acceptor have been studied spectrophotometrically in the chloroform medium. The suggested structures of the solid iodine charge-transfer complexes investigated by several techniques using elemental analysis, mid infrared spectra, and thermal analysis (TGA and DTG) of the solid CT-complexes along with the photometric titration curves for the reactions. The results indicate the formation of two CT-complexes [(D1)]-I(2) and [(D2)]-2I(2) with acceptor:donor molar ratios of 1:1 and 1:2, respectively. The kinetic parameters (non-isothermal method) for their decomposition have been evaluated by graphical methods using the equations of Horowitz-Metzger (HM) and Coats-Redfern (CR). PMID:16920397

  2. Robust, basis-set independent method for the evaluation of charge-transfer energy in noncovalent complexes.

    PubMed

    Řezáč, Jan; de la Lande, Aurélien

    2015-02-10

    Separation of the energetic contribution of charge transfer to interaction energy in noncovalent complexes would provide important insight into the mechanisms of the interaction. However, the calculation of charge-transfer energy is not an easy task. It is not a physically well-defined term, and the results might depend on how it is described in practice. Commonly, the charge transfer is defined in terms of molecular orbitals; in this framework, however, the charge transfer vanishes as the basis set size increases toward the complete basis set limit. This can be avoided by defining the charge transfer in terms of the spatial extent of the electron densities of the interacting molecules, but the schemes used so far do not reflect the actual electronic structure of each particular system and thus are not reliable. We propose a spatial partitioning of the system, which is based on a charge transfer-free reference state, namely superimposition of electron densities of the noninteracting fragments. We show that this method, employing constrained DFT for the calculation of the charge-transfer energy, yields reliable results and is robust with respect to the strength of the charge transfer, the basis set size, and the DFT functional used. Because it is based on DFT, the method is applicable to rather large systems. PMID:26580910

  3. A NEW FRAMEWORK FOR URBAN SUSTAINABILITY ASSESSMENTS: LINKING COMPLEXITY, INFORMATION AND POLICY

    EPA Science Inventory

    Urban systems emerge as distinct entities from the complex interactions among social, economic and cultural attributes, and information, energy and material stocks and flows that operate on different temporal and spatial scales. Such complexity poses a challenge to identify the...

  4. PREFACE: Complex Networks: from Biology to Information Technology

    NASA Astrophysics Data System (ADS)

    Barrat, A.; Boccaletti, S.; Caldarelli, G.; Chessa, A.; Latora, V.; Motter, A. E.

    2008-06-01

    The field of complex networks is one of the most active areas in contemporary statistical physics. Ten years after seminal work initiated the modern study of networks, interest in the field is in fact still growing, as indicated by the ever increasing number of publications in network science. The reason for such a resounding success is most likely the simplicity and broad significance of the approach that, through graph theory, allows researchers to address a variety of different complex systems within a common framework. This special issue comprises a selection of contributions presented at the workshop 'Complex Networks: from Biology to Information Technology' held in July 2007 in Pula (Cagliari), Italy as a satellite of the general conference STATPHYS23. The contributions cover a wide range of problems that are currently among the most important questions in the area of complex networks and that are likely to stimulate future research. The issue is organised into four sections. The first two sections describe 'methods' to study the structure and the dynamics of complex networks, respectively. After this methodological part, the issue proceeds with a section on applications to biological systems. The issue closes with a section concentrating on applications to the study of social and technological networks. The first section, entitled Methods: The Structure, consists of six contributions focused on the characterisation and analysis of structural properties of complex networks: The paper Motif-based communities in complex networks by Arenas et al is a study of the occurrence of characteristic small subgraphs in complex networks. These subgraphs, known as motifs, are used to define general classes of nodes and their communities by extending the mathematical expression of the Newman-Girvan modularity. The same line of research, aimed at characterising network structure through the analysis of particular subgraphs, is explored by Bianconi and Gulbahce in Algorithm

  5. Temporally and spectrally resolved subpicosecond energy transfer within the peripheral antenna complex (LH2) and from LH2 to the core antenna complex in photosynthetic purple bacteria.

    PubMed Central

    Hess, S; Chachisvilis, M; Timpmann, K; Jones, M R; Fowler, G J; Hunter, C N; Sundström, V

    1995-01-01

    We report studies of energy transfer from the 800-nm absorbing pigment (B800) to the 850-nm absorbing pigment (B850) of the LH2 peripheral antenna complex and from LH2 to the core antenna complex (LH1) in Rhodobacter (Rb.) sphaeroides. The B800 to B850 process was studied in membranes from a LH2-reaction center (no LH1) mutant of Rb. sphaeroides and the LH2 to LH1 transfer was studied in both the wild-type species and in LH2 mutants with blue-shifted B850. The measurements were performed by using approximately 100-fs pulses to probe the formation of acceptor excitations in a two-color pump-probe measurement. Our experiments reveal a B800 to B850 transfer time of approximately 0.7 ps at 296 K and energy transfer from LH2 to LH1 is characterized by a time constant of approximately 3 ps at 296 K and approximately 5 ps at 77 K. In the blue-shifted B850 mutants, the transfer time from B850 to LH1 becomes gradually longer with increasing blue-shift of the B850 band as a result of the decreasing spectral overlap between the antennae. The results have been used to produce a model for the association between the ring-like structures that are characteristic of both the LH2 and LH1 antennae. PMID:11607622

  6. The dynamics of information-driven coordination phenomena: A transfer entropy analysis

    PubMed Central

    Borge-Holthoefer, Javier; Perra, Nicola; Gonçalves, Bruno; González-Bailón, Sandra; Arenas, Alex; Moreno, Yamir; Vespignani, Alessandro

    2016-01-01

    Data from social media provide unprecedented opportunities to investigate the processes that govern the dynamics of collective social phenomena. We consider an information theoretical approach to define and measure the temporal and structural signatures typical of collective social events as they arise and gain prominence. We use the symbolic transfer entropy analysis of microblogging time series to extract directed networks of influence among geolocalized subunits in social systems. This methodology captures the emergence of system-level dynamics close to the onset of socially relevant collective phenomena. The framework is validated against a detailed empirical analysis of five case studies. In particular, we identify a change in the characteristic time scale of the information transfer that flags the onset of information-driven collective phenomena. Furthermore, our approach identifies an order-disorder transition in the directed network of influence between social subunits. In the absence of clear exogenous driving, social collective phenomena can be represented as endogenously driven structural transitions of the information transfer network. This study provides results that can help define models and predictive algorithms for the analysis of societal events based on open source data. PMID:27051875

  7. The dynamics of information-driven coordination phenomena: A transfer entropy analysis.

    PubMed

    Borge-Holthoefer, Javier; Perra, Nicola; Gonçalves, Bruno; González-Bailón, Sandra; Arenas, Alex; Moreno, Yamir; Vespignani, Alessandro

    2016-04-01

    Data from social media provide unprecedented opportunities to investigate the processes that govern the dynamics of collective social phenomena. We consider an information theoretical approach to define and measure the temporal and structural signatures typical of collective social events as they arise and gain prominence. We use the symbolic transfer entropy analysis of microblogging time series to extract directed networks of influence among geolocalized subunits in social systems. This methodology captures the emergence of system-level dynamics close to the onset of socially relevant collective phenomena. The framework is validated against a detailed empirical analysis of five case studies. In particular, we identify a change in the characteristic time scale of the information transfer that flags the onset of information-driven collective phenomena. Furthermore, our approach identifies an order-disorder transition in the directed network of influence between social subunits. In the absence of clear exogenous driving, social collective phenomena can be represented as endogenously driven structural transitions of the information transfer network. This study provides results that can help define models and predictive algorithms for the analysis of societal events based on open source data. PMID:27051875

  8. Basic plan and assessment of an information system designed to aid patient transfer.

    PubMed

    Yamamoto, M; Sano, M

    1987-01-01

    One of the important assignments in the planning of community medical care is to find an effective way of implementing the sharing of facilities together with their coordination. In particular, the establishment of a smooth and effective system co-ordinating facilities and functions of medical organizations, comprising clinics and hospitals of various levels, and the installation of an information system, designed to provide positive assistance in information control as well as in its operation, should be undertaken urgently. In this paper, we discuss the patient-transfer system, which is one of the facility-co-ordination-system for medical organizations, from the point of view of total community medical care. Specifically we describe the purpose, features and total structure of the patient-transfer system, and discuss the basic plan for an information system designed to aid patient transfer, from information control together with an advance assessment from the system-engineering point of view. This research has been promoted by the Aichi Medical Association committee for medical care system. The proposed system is planned to be operational in the near future. PMID:3441155

  9. GAM-HEAT -- a computer code to compute heat transfer in complex enclosures. Revision 1

    SciTech Connect

    Cooper, R.E.; Taylor, J.R.; Kielpinski, A.L.; Steimke, J.L.

    1991-02-01

    The GAM-HEAT code was developed for heat transfer analyses associated with postulated Double Ended Guillotine Break Loss Of Coolant Accidents (DEGB LOCA) resulting in a drained reactor vessel. In these analyses the gamma radiation resulting from fission product decay constitutes the primary source of energy as a function of time. This energy is deposited into the various reactor components and is re- radiated as thermal energy. The code accounts for all radiant heat exchanges within and leaving the reactor enclosure. The SRS reactors constitute complex radiant exchange enclosures since there are many assemblies of various types within the primary enclosure and most of the assemblies themselves constitute enclosures. GAM-HEAT accounts for this complexity by processing externally generated view factors and connectivity matrices, and also accounts for convective, conductive, and advective heat exchanges. The code is applicable for many situations involving heat exchange between surfaces within a radiatively passive medium. The GAM-HEAT code has been exercised extensively for computing transient temperatures in SRS reactors with specific charges and control components. Results from these computations have been used to establish the need for and to evaluate hardware modifications designed to mitigate results of postulated accident scenarios, and to assist in the specification of safe reactor operating power limits. The code utilizes temperature dependence on material properties. The efficiency of the code has been enhanced by the use of an iterative equation solver. Verification of the code to date consists of comparisons with parallel efforts at Los Alamos National Laboratory and with similar efforts at Westinghouse Science and Technology Center in Pittsburgh, PA, and benchmarked using problems with known analytical or iterated solutions. All comparisons and tests yield results that indicate the GAM-HEAT code performs as intended.

  10. Direct evidence of energy transfer from a singlet ligand level to lanthanide ions in their diketonate complexes

    NASA Astrophysics Data System (ADS)

    Mironov, L. Yu.; Sveshnikova, E. B.; Ermolaev, V. L.

    2015-07-01

    We have compared the fluorescence intensity of 2-naphthoyltrifluoroacetonate (NTA) in nanoparticles from Gd(NTA)3phen complexes with the fluorescence intensities of this compound in nanoparticles from similar complexes of Pr, Nd, Sm, Eu, Tb, Dy, Er, Ho, and Tm, which absorb in the NTA fluorescence range. We have proven that there is energy transfer from the S 1 level of NTA ligands to Ln(III) ions, which occurs with rates k tr ˜ 1011-1012 s-1. We have also studied the competition between two processes: energy transfer from Ln(NTA)3phen to Ln(III) ions and energy transfer to Nile blue molecules incorporated into nanoparticles from complexes of these ions. It has been shown that, in nanoparticles from complexes of Nd(III), Tb(III), Dy(III), and Tm(III) ions, which are incapable of sensitizing the fluorescence of Nile blue, the values of k tr2 for the energy transfer from NTA to Ln(III) ions, which were obtained from the data on the change in the intensity of the sensitized fluorescence of Nile blue, completely coincide with the values of k tr1 determined from the fluorescence quenching of NTA in these nanoparticles. We have found that, in nanoparticles from Pr, Sm, Eu, Er, and Ho complexes, the efficiency of the sensitized fluorescence of Nile blue is higher than that predicted from the fluorescence quenching of NTA by these ions in their complexes, which indicates that all these ions participate as mediators in the energy transfer from ligands to the dye.

  11. Application of Fisher Information to Complex Dynamic Systems (Tucson)

    EPA Science Inventory

    Fisher information was developed by the statistician Ronald Fisher as a measure of the information obtainable from data being used to fit a related parameter. Starting from the work of Ronald Fisher1 and B. Roy Frieden2, we have developed Fisher information as a measure of order ...

  12. Application of Fisher Information to Complex Dynamic Systems

    EPA Science Inventory

    Fisher information was developed by the statistician Ronald Fisher as a measure of the information obtainable from data being used to fit a related parameter. Starting from the work of Ronald Fisher1 and B. Roy Frieden2, we have developed Fisher information as a measure of order ...

  13. On Rate Limitations of Electron Transfer in the Photosynthetic Cytochrome b6f Complex

    PubMed Central

    Hasan, S. Saif; Cramer, William A.

    2012-01-01

    Considering information in the crystal structures of the cytochrome b6f complex relevant to the rate-limiting step in oxygenic photosynthesis (1–5), it is enigmatic that electron transport in the complex is not limited by the large distance, approximately 26 Å, between the iron-sulfur cluster (ISP) and its electron acceptor, cytochrome f. This enigma has been explained for the respiratory bc1 complex by a crystal structure with a greatly shortened cluster-heme c1 distance (6), leading to a concept of ISP dynamics in which the ISP soluble domain undergoes a translation-rotation conformation change and oscillates between positions relatively close to the cyt c1 heme and a membrane-proximal position close to the ubiquinol electron-proton donor. Comparison of cytochrome b6f structures shows a variation in cytochrome f heme position that suggests the possibility of flexibility and motion of the extended cytochrome f structure that could entail a transient decrease in cluster-heme f distance. The dependence of cyt f turnover on lumen viscosity (7) is consistent with a role of ISP - cyt f dynamics in determination of the rate-limiting step under conditions of low light intensity. Under conditions of low light intensity and proton electrochemical gradient present, for example, under a leaf canopy, it is proposed that a rate limitation of electron transport in the b6f complex may also arise from steric constraints in the entry/exit portal for passage of the plastoquinol and -quinone to/from its oxidation site proximal to the iron-sulfur cluster. PMID:22890107

  14. 36 CFR 1235.20 - How do agencies indicate that transferred records contain information that is restricted from...

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 36 Parks, Forests, and Public Property 3 2014-07-01 2014-07-01 false How do agencies indicate that transferred records contain information that is restricted from public access? 1235.20 Section 1235.20 Parks... agencies indicate that transferred records contain information that is restricted from public access?...

  15. 36 CFR 1235.20 - How do agencies indicate that transferred records contain information that is restricted from...

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 36 Parks, Forests, and Public Property 3 2011-07-01 2011-07-01 false How do agencies indicate that transferred records contain information that is restricted from public access? 1235.20 Section 1235.20 Parks... agencies indicate that transferred records contain information that is restricted from public access?...

  16. 36 CFR 1235.20 - How do agencies indicate that transferred records contain information that is restricted from...

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 36 Parks, Forests, and Public Property 3 2012-07-01 2012-07-01 false How do agencies indicate that transferred records contain information that is restricted from public access? 1235.20 Section 1235.20 Parks... agencies indicate that transferred records contain information that is restricted from public access?...

  17. 48 CFR 52.232-35 - Designation of Office for Government Receipt of Electronic Funds Transfer Information.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... Government Receipt of Electronic Funds Transfer Information. 52.232-35 Section 52.232-35 Federal Acquisition... CONTRACT CLAUSES Text of Provisions and Clauses 52.232-35 Designation of Office for Government Receipt of Electronic Funds Transfer Information. As prescribed in 32.1110(c), insert the following clause:...

  18. Mixing of exciton and charge-transfer states in light-harvesting complex Lhca4.

    PubMed

    Novoderezhkin, Vladimir I; Croce, Roberta; Wahadoszamen, Md; Polukhina, Iryna; Romero, Elisabet; van Grondelle, Rienk

    2016-07-28

    Lhca4 is one of the peripheral antennae of higher plant photosystem I and it is characterized by the presence of chlorophyll a with absorption and emission bands around 30 nm red-shifted compared to those of the other chlorophylls associated with plant complexes. In this work we have investigated the origin of this red shift by using the recent structure of Lhca4 (Qin et al., Science, 2015, 348, 989) to build an exciton model that includes a charge-transfer (CT) state mixed with the excited-state manifold. A simultaneous quantitative fit of absorption, linear dichroism, fluorescence, and Stark absorption spectra of the wild-type Lhca4 and NH mutant (where the sites involved in CT are affected) enables us to determine the origin of the CT state and explore its spectral signatures. A huge borrowing of dipole strength by the CT, accompanied by anomalous broadening and red-shifting of the fluorescence as well as dramatic changes in the Stark spectrum, can be accounted for by a model implying an exciton-type mixing between excited states and CT states. PMID:27375175

  19. Conductive PVDF-HFP nanofibers with embedded TTF-TCNQ charge transfer complex.

    PubMed

    Gal-Oz, Reshef; Patil, Nilesh; Khalfin, Rafail; Cohen, Yachin; Zussman, Eyal

    2013-07-10

    Tetrathiafulvalene-tetracyanoquinodimethane charge-transfer complex (TTF-TCNQ CTC) represents a promising organic conductive system. However, application of this donor-acceptor pair is highly limited, because of its ultrafast crystallization kinetics and very low solubility. In this work, conductive organic nanofibers were generated via a coelectrospinning process of poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) with embedded TTF and TCNQ in the shell and core solutions, respectively. Upon supply of the polymer solutions, a core-shell droplet was formed at the exit of the spinneret. The electron donor TTF and the electron acceptor TCNQ migrated toward each other, within the compound droplet, to produce conductive CTC crystals. In the presence of a sufficiently strong electric field, jetting set in at the droplet tip, which yielded solidified PVDF-HFP nanofibers embedded with aligned CTC. Fiber diameters ranged between 100 and 500 nm. X-ray analysis showed strong equatorial reflections (110,200) of oriented copolymer PVDF-HFP crystals (β-phase) with copolymer chains oriented along the fiber axis, and of CTC (001), indicating that the CTC molecular planes were aligned parallel to the nanofiber axis. In addition, reflections of unreacted TCNQ (120,220) and TTF (110) crystals were observed. The electrospun nanofibers were collected to form a fiber mat, which was evaluated as a working electrode in a three-electrode cell system, exhibiting differential conductance of 5.23 μmho. PMID:23745509

  20. A Synthetic Oxygen Atom Transfer Photocycle from a Diruthenium Oxyanion Complex.

    PubMed

    Corcos, Amanda R; Pap, József S; Yang, Tzuhsiung; Berry, John F

    2016-08-10

    Three new diruthenium oxyanion complexes have been prepared, crystallographically characterized, and screened for their potential to photochemically unmask a reactive Ru-Ru═O intermediate. The most promising candidate, Ru2(chp)4ONO2 (4, chp = 6-chloro-2-hydroxypyridinate), displays a set of signals centered around m/z = 733 amu in its MALDI-TOF mass spectrum, consistent with the formation of the [Ru2(chp)4O](+) ([6](+)) ion. These signals shift to 735 amu in 4*, which contains an (18)O-labeled nitrate. EPR spectroscopy and headspace GC-MS analysis indicate that NO2(•) is released upon photolysis of 4, also consistent with the formation of 6. Photolysis of 4 in CH2Cl2 at room temperature in the presence of excess PPh3 yields OPPh3 in 173% yield; control experiments implicate 6, NO2(•), and free NO3(-) as the active oxidants. Notably, Ru2(chp)4Cl (3) is recovered after photolysis. Since 3 is the direct precursor to 4, the results described herein constitute the first example of a synthetic cycle for oxygen atom transfer that makes use of light to generate a putative metal oxo intermediate. PMID:27406958