Science.gov

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. 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.

  3. 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

  4. New Information Transfer Therapies

    ERIC Educational Resources Information Center

    Lorenzi, Nancy M.; Young, K. Penny

    1974-01-01

    Specific examples of dial access systems, information centers, computer assisted instruction for students, use of media communication, resource centers, and library consortia in the biomedical field. (LS)

  5. 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

  6. 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.

  7. Information Networks: Definitions and Message Transfer Models.

    ERIC Educational Resources Information Center

    Nance, Richard E.; And Others

    A mathematical definition of an information network is constructed with the purpose of developing a theory useful in answering practical questions concerning information transfer. An information network includes: (1) users, (2) information resources, (3) information centers, and (4) the total information transfer structure linking (1), (2), and…

  8. 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.

  9. 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.…

  10. 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.

  11. 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.

  12. 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.

  13. Information complexity of neural networks.

    PubMed

    Kon, M A; Plaskota, L

    2000-04-01

    This paper studies the question of lower bounds on the number of neurons and examples necessary to program a given task into feed forward neural networks. We introduce the notion of information complexity of a network to complement that of neural complexity. Neural complexity deals with lower bounds for neural resources (numbers of neurons) needed by a network to perform a given task within a given tolerance. Information complexity measures lower bounds for the information (i.e. number of examples) needed about the desired input-output function. We study the interaction of the two complexities, and so lower bounds for the complexity of building and then programming feed-forward nets for given tasks. We show something unexpected a priori--the interaction of the two can be simply bounded, so that they can be studied essentially independently. We construct radial basis function (RBF) algorithms of order n3 that are information-optimal, and give example applications.

  14. 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.

  15. 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)

  16. 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.

  17. 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

  18. Darwinian demons, evolutionary complexity, and information maximization

    NASA Astrophysics Data System (ADS)

    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.

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. 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.

  5. Threshold fatigue and information transfer

    PubMed Central

    Lindner, Benjamin; Longtin, André

    2016-01-01

    Neurons in vivo must process sensory information in the presence of significant noise. It is thus plausible to assume that neural systems have developed mechanisms to reduce this noise. Theoretical studies have shown that threshold fatigue (i.e. cumulative increases in the threshold during repetitive firing) could lead to noise reduction at certain frequencies bands and thus improved signal transmission as well as noise increases and decreased signal transmission at other frequencies: a phenomenon called noise shaping. There is, however, no experimental evidence that threshold fatigue actually occurs and, if so, that it will actually lead to noise shaping. We analyzed action potential threshold variability in intracellular recordings in vivo from pyramidal neurons in weakly electric fish and found experimental evidence for threshold fatigue: an increase in instantaneous firing rate was on average accompanied by an increase in action potential threshold. We show that, with a minor modification, the standard Hodgkin–Huxley model can reproduce this phenomenon. We next compared the performance of models with and without threshold fatigue. Our results show that threshold fatigue will lead to a more regular spike train as well as robustness to intrinsic noise via noise shaping. We finally show that the increased/reduced noise levels due to threshold fatigue correspond to decreased/increased information transmission at different frequencies. PMID:17436067

  6. 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

  7. Conscious attention, meditation, and bilateral information transfer.

    PubMed

    Bob, Petr; Zimmerman, Elizabeth M; Hamilton, Elizabeth A; Sheftel, Jenna G; Bajo, Stephanie D; Raboch, Jiri; Golla, Megan; Konopka, Lukasz M

    2013-01-01

    Recent findings indicate that conscious attention is related to large-scale information integration of various brain regions, including both hemispheres, that enables integration of parallel distributed modalities of processed information. There is also evidence that the level of information transference related to integration or splitting among brain regions, and between hemispheres, establishes a certain level of efficiency of the information processing. The level of information transference also may have modulatory influences on attentional capacity that are closely linked to the emotional arousal and autonomic response related to a stimulus. These findings suggest a hypothesis that changes in conscious attention, specifically during meditation could be reflected in the autonomic activity as the left-right information transference calculated from bilateral electrodermal activity (EDA). With the aim to compare conscious attention during meditation with other attentional states (resting state, Stroop task, and memory task), we performed bilateral EDA measurement in 7 healthy persons during resting state, Stroop task, neurofeedback memory test, and meditation. The results indicate that the information transference (ie, transinformation) is able to distinguish those attentional states, and that the highest level of the transinformation has been found during attentional processing related to meditation, indicating higher level of connectivity between left and right sides. Calculations other than pointwise transinformation (PTI) performed on EDA records, such as mean skin conductance level or laterality index, were not able to distinguish attentional states. The results suggest that PTI may present an interesting method useful for the assessment of information flow, related to neural functioning, that in the case of meditation may reflect typical integrative changes in the autonomic nervous system related to brain functions and focused attentional processing.

  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. 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.

  10. 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

  11. 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.

  12. 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

  13. 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.

  14. 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.

  15. 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...

  16. 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...

  17. 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...

  18. 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...

  19. 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...

  20. 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.

  1. 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.

  2. 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

  3. 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.

  4. Bilateral Transfer: The Effects of Practice on the Transfer of Complex Dance Movement Patterns.

    ERIC Educational Resources Information Center

    Puretz, Susan L.

    1983-01-01

    The effects of practice on the bilateral transfer of complex dance movement patterns were studied by having subjects learn two sequences under eight different conditions. Results indicate that teachers have been correct in expecting students to transfer movements bilaterally (from one side to the other) but should teach to the nonpreferred side.…

  5. The Transfer Achievement Program (TAP): Information Packet.

    ERIC Educational Resources Information Center

    Segura, Armando; Noseworthy, Victoria

    Santa Barbara City College (California) created the Transfer Achievement Program (TAP) to deliver an integrated and cohesive set of services to underrepresented students to help increase their transfer rate to four-year institutions. TAP provides students with a developmental map of transfer-related activities through the use of the Transfer Task…

  6. Transfer: Key to the Master Plan. Information Agenda Item 1.

    ERIC Educational Resources Information Center

    Kerschner, Lee R.; Lindahl, Charles W.

    Focusing on the role of the California State University (CSU) in renewing and strengthening the transfer function, this report includes information on the history and importance of transfer, low transfer rates and other problems, CSU and cooperative efforts to improve transfer, and joint plans of the CSU and the state's community colleges to…

  7. Complexity measurement based on information theory and kolmogorov complexity.

    PubMed

    Lui, Leong Ting; Terrazas, Germán; Zenil, Hector; Alexander, Cameron; Krasnogor, Natalio

    2015-01-01

    In the past decades many definitions of complexity have been proposed. Most of these definitions are based either on Shannon's information theory or on Kolmogorov complexity; these two are often compared, but very few studies integrate the two ideas. In this article we introduce a new measure of complexity that builds on both of these theories. As a demonstration of the concept, the technique is applied to elementary cellular automata and simulations of the self-organization of porphyrin molecules.

  8. Parallel information transfer in a multinode quantum information processor.

    PubMed

    Borneman, T W; Granade, C E; Cory, D G

    2012-04-01

    We describe a method for coupling disjoint quantum bits (qubits) in different local processing nodes of a distributed node quantum information processor. An effective channel for information transfer between nodes is obtained by moving the system into an interaction frame where all pairs of cross-node qubits are effectively coupled via an exchange interaction between actuator elements of each node. All control is achieved via actuator-only modulation, leading to fast implementations of a universal set of internode quantum gates. The method is expected to be nearly independent of actuator decoherence and may be made insensitive to experimental variations of system parameters by appropriate design of control sequences. We show, in particular, how the induced cross-node coupling channel may be used to swap the complete quantum states of the local processors in parallel.

  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. Mechanisms of ubiquitin transfer by the anaphase-promoting complex

    PubMed Central

    2009-01-01

    The anaphase-promoting complex (APC) is a ubiquitin-protein ligase required for the completion of mitosis in all eukaryotes. Recent mechanistic studies reveal how this remarkable enzyme combines specificity in substrate binding with flexibility in ubiquitin transfer, thereby allowing the modification of multiple lysines on the substrate as well as specific lysines on ubiquitin itself. PMID:19874575

  11. 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...

  12. 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...

  13. 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...

  14. 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...

  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. 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

  17. On the planetary and Milne problems in complex radiative transfer

    NASA Astrophysics Data System (ADS)

    Viik, T.

    2016-11-01

    In this paper we consider two classical problems in radiative transfer - the planetary and the Milne problems - in an isotropic homogeneous optically semi-infinite medium where the albedo of single scattering may be defined anywhere in the complex plane. It appeared that the method of approximating the kernel in the integral equation for the Sobolev resolvent function can be used even in such a case. This approach allows to express almost all the relevant functions of transfer for those problems by simply determinable auxiliary functions.

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. Information Transfer Analysis of Spontaneous Low-frequency Fluctuations in Cerebral Hemodynamics and Cardiovascular Dynamics

    NASA Astrophysics Data System (ADS)

    Katura, Takusige; Tanaka, Naoki; Obata, Akiko; Sato, Hiroki; Maki, Atsushi

    2005-08-01

    In this study, from the information-theoretic viewpoint, we analyzed the interrelation between the spontaneous low-frequency fluctuations around 0.1Hz in the hemoglobin concentration in the cerebral cortex, mean arterial blood pressure and the heart rate. For this analysis, as measures of information transfer, we used transfer entropy (TE) proposed for two-factor systems by Schreiber and intrinsic transfer entropy (ITE) introduced for further analysis of three-factor systems by extending the original TE. In our analysis, information transfer analysis based on both TE and ITE suggests the systemic cardiovascular fluctuations alone cannot account for the cerebrovascular fluctuations, that is, the regulation of the regional cerebral energetic metabolism is important as a candidate of its generation mechanism Such an information transfer analysis seems useful to reveal the interrelation between the elements regulated each other in a complex manner.

  3. 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…

  4. 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.

  5. 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.

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

    PubMed

    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

    2011-08-01

    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

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

    PubMed

    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

    2011-08-01

    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.

  8. 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

  9. 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

  10. 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

  11. 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.

  12. 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.

  13. 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

  14. 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…

  15. 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.

  16. 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.

  17. 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.

  18. Scientific Information Transfer and National Development in Africa.

    ERIC Educational Resources Information Center

    Adimorah, E. N. O.

    1978-01-01

    Examines the potential of scientific information transfer in selected English- and Arab-speaking countries of Africa, as it relates to national development through socio-economic planning, agriculture, medicine, and science and technology. (Author/CWM)

  19. 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

  20. 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.

  1. 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

  2. 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.

  3. 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.

  4. 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).

  5. 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.

  6. 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…

  7. 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.

  8. 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

  9. 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

  10. NHC-manganese(i) complexes as carbene transfer agents.

    PubMed

    Ruiz, Javier; Berros, Angela; Perandones, Bernabé F; Vivanco, Marilín

    2009-09-21

    Tautomerization of coordinated azoles to their corresponding N-heterocyclic carbenes (NHCs) has been carried out by reaction of complexes fac-[Mn(L)(CO)(3)(dppe)](+) (L = N-phenylimidazole) and fac-[Mn(L)(CO)(3)(bipy)](+) (L = N-methylbenzimidazole, benzoxazole, benzothiazole) with KO(t)Bu and subsequent protonation of the azolyl intermediates with NH(4)PF(6). Several NHC-manganese(i) complexes bearing an N-H residue of general formula fac-[Mn(NHC)(CO)(3)(dppe)](+) and fac-[Mn(NHC)(CO)(3)(bipy)](+) have been tested as carbene transfer agents to the gold fragments [Au(L)](+) (L = PPh(3), CNPh, CNXylyl), allowing isolation or spectroscopic detection of various Mn(i)/Au(i) heterometallic intermediates containing azolyl bridging ligands, which liberate the gold(i) carbene complexes [Au(NHC)(L)](+) by means of acid hydrolysis. By contrast, when using the silver(i) fragment [Ag(PPh(3))](+) as carbene acceptor no transmetallation process occurred but instead inverse tautomerization of the NHC to the corresponding imidazole ligand was observed.

  11. 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.

  12. 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.…

  13. Energy Information Transfer in Virginia. A Planning Conference.

    ERIC Educational Resources Information Center

    Hickin, Patricia

    The Virginia Planning Conference for Solar Technology Information Transfer was held in Richmond in February 1978 to elicit suggestions on how to make Virginians aware of libraries as sources of energy information and how Virginia libraries can keep their energy materials and reference services up to date. A summary of this planning session and a…

  14. 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.

  15. 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.

  16. 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.

  17. 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…

  18. 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.

  19. 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.

  20. 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

  1. Non-Ergodic Electron Transfer in Mixed-Valence Charge-Transfer Complexes.

    PubMed

    Matyushov, Dmitry V

    2012-06-21

    Theories of activated transitions traditionally separate the dynamics and statistics of the thermal bath in the reaction rate into the preexponential frequency factor for the dynamics and a Boltzmann factor for the statistics. When the reaction rate is comparable to relaxation frequencies of the medium, the statistics loses ergodicity and the activation barrier becomes dependent on the medium dynamics. This scenario is realized for mixed-valence self-exchange electron transfer at temperatures near the point of solvent crystallization. These complexes, studied by Kubiak and coworkers, display anti-Arrhenius temperature dependence on lowering temperature when approaching crystallization; that is, the reaction rate increases nonlinearly in Arrhenius coordinates. Accordingly, the solvent relaxation slows down following a power temperature law. With this functional form for the relaxation time, nonergodic reaction kinetics accounts well for the observations.

  2. Information transfer during contingency operations: Emergency air-ground communications

    NASA Technical Reports Server (NTRS)

    Porter, R. F.

    1981-01-01

    Safety related problems are reported which occur as a consequence of information transfer deficiencies that arise when air/ground communications are (or should be) used as a resource in inflight emergency situations. The system factors, the human errors, and the associated causes of these problem are defined.

  3. Transfer of Information from Short- to Long-Term Memory

    ERIC Educational Resources Information Center

    Modigliani, Vito; Seamon, John G.

    1974-01-01

    The present study examined current hypotheses concerning information transfer from short-term memory (STM) to long-term memory (LTM) using a Peterson STM task with word triplets presented over retention intervals of 0, 3, 6, 9, and 18 sec. (Editor)

  4. 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…

  5. Workshop on Possibilities for Improving Information Transfer. Final Report.

    ERIC Educational Resources Information Center

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

    Presented are the proceedings from a workshop held in Rabat, Morocco from May 24-28, 1976. The main objective of the workshop was to evaluate progress made in information transfer and prepare a program of action enabling documentation centers created or assisted by UNESCO to cooperate in such areas as staff training, translation activities, and…

  6. 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)

  7. Transgenerational epigenetic inheritance: focus on soma to germline information transfer.

    PubMed

    Sharma, Abhay

    2013-12-01

    In trangenerational epigenetic inheritance, phenotypic information not encoded in DNA sequence is transmitted across generations. In germline-dependent mode, memory of environmental exposure in parental generation is transmitted through gametes, leading to appearance of phenotypes in the unexposed future generations. The memory is considered to be encoded in epigenetic factors like DNA methylation, histone modifications and regulatory RNAs. Environmental exposure may cause epigenetic modifications in the germline either directly or indirectly through primarily affecting the soma. The latter possibility is most intriguing because it contradicts the established dogma that hereditary information flows only from germline to soma, not in reverse. As such, identification of the factor(s) mediating soma to germline information transfer in transgenerational epigenetic inheritance would be pathbreaking. Regulatory RNAs and hormone have previously been implicated or proposed to play a role in soma to germline communication in epigenetic inheritance. This review examines the recent examples of gametogenic transgenerational inheritance in plants and animals in order to assess if evidence of regulatory RNAs and hormones as mediators of information transfer is supported. Overall, direct evidence for both mobile regulatory RNAs and hormones is found to exist in plants. In animals, although involvement of mobile RNAs seems imminent, direct evidence of RNA-mediated soma to germline information transfer in transgenerational epigenetic inheritance is yet to be obtained. Direct evidence is also lacking for hormones in animals. However, detailed examination of recently reported examples of transgenerational inheritance reveals circumstantial evidence supporting a role of hormones in information transmission.

  8. 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

  9. Measuring information transfer in a soft robotic arm.

    PubMed

    Nakajima, K; Schmidt, N; Pfeifer, R

    2015-05-13

    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.

  10. 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.

  11. Lag-specific transfer entropy as a tool to assess cardiovascular and cardiorespiratory information transfer.

    PubMed

    Faes, Luca; Marinazzo, Daniele; Montalto, Alessandro; Nollo, Giandomenico

    2014-10-01

    In the study of interacting physiological systems, model-free tools for time series analysis are fundamental to provide a proper description of how the coupling among systems arises from the multiple involved regulatory mechanisms. This study presents an approach which evaluates direction, magnitude, and exact timing of the information transfer between two time series belonging to a multivariate dataset. The approach performs a decomposition of the well-known transfer entropy (TE) which achieves 1) identifying, according to a lag-specific information-theoretic formulation of the concept of Granger causality, the set of time lags associated with significant information transfer, and 2) assigning to these delays an amount of information transfer such that the total contribution yields the aggregate TE. The approach is first validated on realizations of simulated linear and nonlinear multivariate processes interacting at different time lags and with different strength, reporting a high accuracy in the detection of imposed delays, and showing that the estimated lag-specific TE follows the imposed coupling strength. The subsequent application to heart period, systolic arterial pressure and respiration variability series measured from healthy subjects during a tilt test protocol illustrated how the proposed approach quantifies the modifications in the involvement and latency of important mechanisms of short-term physiological regulation, like the baroreflex and the respiratory sinus arrhythmia, induced by the orthostatic stress.

  12. 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.

  13. Compositional genomes: prebiotic information transfer in mutually catalytic noncovalent assemblies.

    PubMed

    Segré, D; Ben-Eli, D; Lancet, D

    2000-04-11

    Mutually catalytic sets of simple organic molecules have been suggested to be capable of self-replication and rudimentary chemical evolution. Previous models for the behavior of such sets have analyzed the global properties of short biopolymer ensembles by using graph theory and a mean field approach. In parallel, experimental studies with the autocatalytic formation of amphiphilic assemblies (e.g., lipid vesicles or micelles) demonstrated self-replication properties resembling those of living cells. Combining these approaches, we analyze here the kinetic behavior of small heterogeneous assemblies of spontaneously aggregating molecules, of the type that could form readily under prebiotic conditions. A statistical formalism for mutual rate enhancement is used to numerically simulate the detailed chemical kinetics within such assemblies. We demonstrate that a straightforward set of assumptions about kinetically enhanced recruitment of simple amphiphilic molecules, as well as about the spontaneous growth and splitting of assemblies, results in a complex population behavior. The assemblies manifest a significant degree of homeostasis, resembling the previously predicted quasi-stationary states of biopolymer ensembles (Dyson, F. J. (1982) J. Mol. Evol. 18, 344-350). Such emergent catalysis-driven, compositionally biased entities may be viewed as having rudimentary "compositional genomes." Our analysis addresses the question of how mutually catalytic metabolic networks, devoid of sequence-based biopolymers, could exhibit transfer of chemical information and might undergo selection and evolution. This computed behavior may constitute a demonstration of natural selection in populations of molecules without genetic apparatus, suggesting a pathway from random molecular assemblies to a minimal protocell. PMID:10760281

  14. Compositional genomes: Prebiotic information transfer in mutually catalytic noncovalent assemblies

    PubMed Central

    Segré, Daniel; Ben-Eli, Dafna; Lancet, Doron

    2000-01-01

    Mutually catalytic sets of simple organic molecules have been suggested to be capable of self-replication and rudimentary chemical evolution. Previous models for the behavior of such sets have analyzed the global properties of short biopolymer ensembles by using graph theory and a mean field approach. In parallel, experimental studies with the autocatalytic formation of amphiphilic assemblies (e.g., lipid vesicles or micelles) demonstrated self-replication properties resembling those of living cells. Combining these approaches, we analyze here the kinetic behavior of small heterogeneous assemblies of spontaneously aggregating molecules, of the type that could form readily under prebiotic conditions. A statistical formalism for mutual rate enhancement is used to numerically simulate the detailed chemical kinetics within such assemblies. We demonstrate that a straightforward set of assumptions about kinetically enhanced recruitment of simple amphiphilic molecules, as well as about the spontaneous growth and splitting of assemblies, results in a complex population behavior. The assemblies manifest a significant degree of homeostasis, resembling the previously predicted quasi-stationary states of biopolymer ensembles (Dyson, F. J. (1982) J. Mol. Evol. 18, 344–350). Such emergent catalysis-driven, compositionally biased entities may be viewed as having rudimentary “compositional genomes.” Our analysis addresses the question of how mutually catalytic metabolic networks, devoid of sequence-based biopolymers, could exhibit transfer of chemical information and might undergo selection and evolution. This computed behavior may constitute a demonstration of natural selection in populations of molecules without genetic apparatus, suggesting a pathway from random molecular assemblies to a minimal protocell. PMID:10760281

  15. 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.

  16. 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

  17. 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.

  18. A complex network model for seismicity based on mutual information

    NASA Astrophysics Data System (ADS)

    Jiménez, Abigail

    2013-05-01

    Seismicity is the product of the interaction between the different parts of the lithosphere. Here, we model each part of the Earth as a cell that is constantly communicating its state to its environment. As a neuron is stimulated and produces an output, the different parts of the lithosphere are constantly stimulated by both other cells and the ductile part of the lithosphere, and produce an output in the form of a stress transfer or an earthquake. This output depends on the properties of each part of the Earth’s crust and the magnitude of the inputs. In this study, we propose an approach to the quantification of this communication, with the aid of the Information Theory, and model seismicity as a Complex Network. We have used data from California, and this new approach gives a better understanding of the processes involved in the formation of seismic patterns in that region.

  19. Solvation-driven charge transfer and localization in metal complexes.

    PubMed

    Rondi, Ariana; Rodriguez, Yuseff; Feurer, Thomas; Cannizzo, Andrea

    2015-05-19

    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 stabilization of CT

  20. 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.

  1. 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.

  2. 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

  3. 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.

  4. 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

  5. Carotenoid to chlorophyll energy transfer in the peridinin–chlorophyll-a–protein complex involves an intramolecular charge transfer state

    PubMed Central

    Zigmantas, Donatas; Hiller, Roger G.; Sundström, Villy; Polívka, Tomáš

    2002-01-01

    Carotenoids are, along with chlorophylls, crucial pigments involved in light-harvesting processes in photosynthetic organisms. Details of carotenoid to chlorophyll energy transfer mechanisms and their dependence on structural variability of carotenoids are as yet poorly understood. Here, we employ femtosecond transient absorption spectroscopy to reveal energy transfer pathways in the peridinin–chlorophyll-a–protein (PCP) complex containing the highly substituted carotenoid peridinin, which includes an intramolecular charge transfer (ICT) state in its excited state manifold. Extending the transient absorption spectra toward near-infrared region (600–1800 nm) allowed us to separate contributions from different low-lying excited states of peridinin. The results demonstrate a special light-harvesting strategy in the PCP complex that uses the ICT state of peridinin to enhance energy transfer efficiency. PMID:12486228

  6. 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.

  7. Information transfer and behavioural inertia in starling flocks

    NASA Astrophysics Data System (ADS)

    Attanasi, Alessandro; Cavagna, Andrea; Del Castello, Lorenzo; Giardina, Irene; Grigera, Tomas S.; Jelić, Asja; Melillo, Stefania; Parisi, Leonardo; Pohl, Oliver; Shen, Edward; Viale, Massimiliano

    2014-09-01

    Collective decision-making in biological systems requires all individuals in the group to go through a behavioural change of state. During this transition fast and robust transfer of information is essential to prevent cohesion loss. The mechanism by which natural groups achieve such robustness, however, is not clear. Here we present an experimental study of starling flocks performing collective turns. We find that information about direction changes propagates across the flock with a linear dispersion law and negligible attenuation, hence minimizing group decoherence. These results contrast starkly with present models of collective motion, which predict diffusive transport of information. Building on spontaneous symmetry breaking and conservation-law arguments, we formulate a theory that correctly reproduces linear and undamped propagation. Essential to this framework is the inclusion of the birds' behavioural inertia. The theory not only explains the data, but also predicts that information transfer must be faster the stronger the group's orientational order, a prediction accurately verified by the data. Our results suggest that swift decision-making may be the adaptive drive for the strong behavioural polarization observed in many living groups.

  8. Information transfer and behavioural inertia in starling flocks.

    PubMed

    Attanasi, Alessandro; Cavagna, Andrea; Del Castello, Lorenzo; Giardina, Irene; Grigera, Tomas S; Jelić, Asja; Melillo, Stefania; Parisi, Leonardo; Pohl, Oliver; Shen, Edward; Viale, Massimiliano

    2014-09-01

    Collective decision-making in biological systems requires all individuals in the group to go through a behavioural change of state. During this transition fast and robust transfer of information is essential to prevent cohesion loss. The mechanism by which natural groups achieve such robustness, though, is not clear. Here we present an experimental study of starling flocks performing collective turns. We find that information about direction changes propagates across the flock with a linear dispersion law and negligible attenuation, hence minimizing group decoherence. These results contrast starkly with current models of collective motion, which predict diffusive transport of information. Building on spontaneous symmetry breaking and conservation laws arguments, we formulate a new theory that correctly reproduces linear and undamped propagation. Essential to the new framework is the inclusion of the birds' behavioural inertia. The new theory not only explains the data, but also predicts that information transfer must be faster the stronger the group's orientational order, a prediction accurately verified by the data. Our results suggest that swift decision-making may be the adaptive drive for the strong behavioural polarization observed in many living groups. PMID:25264452

  9. Nonlocal Quantum Information Transfer Without Superluminal Signalling and Communication

    NASA Astrophysics Data System (ADS)

    Walleczek, Jan; Grössing, Gerhard

    2016-09-01

    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

  10. 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

  11. Genetic Redundancies Enhance Information Transfer in Noisy Regulatory Circuits

    PubMed Central

    Rodrigo, Guillermo; Poyatos, Juan F.

    2016-01-01

    Cellular decision making is based on regulatory circuits that associate signal thresholds to specific physiological actions. This transmission of information is subjected to molecular noise what can decrease its fidelity. Here, we show instead how such intrinsic noise enhances information transfer in the presence of multiple circuit copies. The result is due to the contribution of noise to the generation of autonomous responses by each copy, which are altogether associated with a common decision. Moreover, factors that correlate the responses of the redundant units (extrinsic noise or regulatory cross-talk) contribute to reduce fidelity, while those that further uncouple them (heterogeneity within the copies) can lead to stronger information gain. Overall, our study emphasizes how the interplay of signal thresholding, redundancy, and noise influences the accuracy of cellular decision making. Understanding this interplay provides a basis to explain collective cell signaling mechanisms, and to engineer robust decisions with noisy genetic circuits. PMID:27741249

  12. Conducting molecular nanostructures assembled from charge-transfer complexes grafted onto silicon surfaces

    NASA Astrophysics Data System (ADS)

    Stires, John C., IV; Kasibhatla, Bala S. T.; Siegel, Dustin S.; Kwong, Jinny C.; Caballero, Jonathan B.; Labonte, Andre P.; Reifenberger, Ronald G.; Datta, Supriyo; Kubiak, Clifford P.

    2003-12-01

    Heterodimeric electon-donor/electron-acceptor charge-transfer complexes chemisorbed onto Au(111) by attachment of the electron-donor to the surface have been characterized by scanning tunneling microscopy and Kelvin probe experiments. Conductance measurements exhibit nearly Ohmic I(V) responses at low bias. The electrical properties of the charge-transfer complex are vastly different than those of the electron-donor alone which exhibits insulating behavior at low bias. In an extension of this work, strategies are being developed for attachment of charge-transfer complexes to semiconducting or insulating surfaces. Fabrication of nanoscale molecular electronic devices is being investigated by attaching one component of a charge-transfer complex to a silicon surface by chemically directed self-assembly. The single component-functionalized surface is then used as a substrate on which the second component of the charge-transfer complex is deposited by the atomic force microscopy method, dip-pen nanolithography (DPN). Derivatives of hexamethylbenze (electron-donor) with terminal olefins attached to crystalline silicon surfaces via hydrosilylation form monolayer-functionalized silicon surfaces that are expected to have insulating properties. Well-defined features can be "drawn" onto the donor-functionalized surfaces by DPN using tetracyanoethylene (electron-acceptor) as the "ink." The resulting charge-transfer complex nanostructures have conducting properties suitable for device function and are flanked by an insulating monolayer, thus creating "wires" made from charge-transfer complexes.

  13. 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

  14. 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.

  15. Synthesis, characterisation, and oxygen atom transfer reactions involving the first gold(I)-alkylperoxo complexes.

    PubMed

    Collado, Alba; Gómez-Suárez, Adrián; Oonishi, Yoshihiro; Slawin, Alexandra M Z; Nolan, Steven P

    2013-11-25

    The synthesis of a new class of organogold species containing a peroxo moiety is reported. Complexes [Au(IPr)(OO(t)Bu)] and [Au(SIPr)(OO(t)Bu)] have been synthesised via a straightforward methodology using the parent gold(I) hydroxide complexes as synthons. These complexes have been successfully used in oxygen-transfer reactions to triphenylphosphine.

  16. The formation of bifurcated charge transfer complexes with molecular iodine

    NASA Astrophysics Data System (ADS)

    Kulevsky, Norman; Pierce, Ken

    1993-03-01

    I 2 complexes with triptycene and several di- and triaryl derivatives of methane and ethane were studied. For these complexes the values of λ CT are virtually identical to those reported for the complexes with the analogous monoaryl donors, while the values of λ for their blue shifted I 2 peaks are significantly lower than those for the monoaryl complexes. Both the equilibrium constants and - ΔH 0 values for the formation of complexes from the components lead to the conclusion that the complexes with the di- and triaryl compounds are more stable than those with the monoaryl donors. For the diaryl donors, the Δ S0298 values for complex formation are less favorable than those of the monoaryl donors. The dipole moment for I 2 in diphenylmethane is larger than the moment of I 2 in toluene. All of these observations can be explained by taking into account the transannular effect of one aromatic ring on another and viewing the complexes as bifurcated ones in which the I atom at one end of an I 2 molecule simultaneously interacts with two rings in the donor molecules.

  17. Enhanced electron-transfer reactivity of nonheme manganese(IV)-oxo complexes by binding scandium ions.

    PubMed

    Yoon, Heejung; Lee, Yong-Min; Wu, Xiujuan; Cho, Kyung-Bin; Sarangi, Ritimukta; Nam, Wonwoo; Fukuzumi, Shunichi; Fuhkuzumi, Shunichi

    2013-06-19

    One and two scandium ions (Sc(3+)) are bound strongly to nonheme manganese(IV)-oxo complexes, [(N4Py)Mn(IV)(O)](2+) (N4Py = N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine) and [(Bn-TPEN)Mn(IV)(O)](2+) (Bn-TPEN = N-benzyl-N,N',N'-tris(2-pyridylmethyl)-1,2-diaminoethane), to form Mn(IV)(O)-(Sc(3+))1 and Mn(IV)(O)-(Sc(3+))2 complexes, respectively. The binding of Sc(3+) ions to the Mn(IV)(O) complexes was examined by spectroscopic methods as well as by DFT calculations. The one-electron reduction potentials of the Mn(IV)(O) complexes were markedly shifted to a positive direction by binding of Sc(3+) ions. Accordingly, rates of the electron transfer reactions of the Mn(IV)(O) complexes were enhanced as much as 10(7)-fold by binding of two Sc(3+) ions. The driving force dependence of electron transfer from various electron donors to the Mn(IV)(O) and Mn(IV)(O)-(Sc(3+))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 Mn(IV)(O)-(Sc(3+))2 complexes resulted in remarkable enhancement of the electron-transfer reactivity of the Mn(IV)(O) complexes. Such a dramatic enhancement of the electron-transfer reactivity of the Mn(IV)(O) complexes by binding of Sc(3+) ions resulted in the change of mechanism in the sulfoxidation of thioanisoles by Mn(IV)(O) complexes from a direct oxygen atom transfer pathway without metal ion binding to an electron-transfer pathway with binding of Sc(3+) ions.

  18. 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.

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

    PubMed

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

    2015-02-12

    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.

  20. 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

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

    PubMed Central

    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

  2. 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.

  3. Fisher Information and Complexity Measure of Generalized Morse Potential Model

    NASA Astrophysics Data System (ADS)

    Onate, C. A.; Idiodi, J. O. A.

    2016-09-01

    The spreading of the quantum-mechanical probability distribution density of the three-dimensional system is quantitatively determined by means of the local information-theoretic quantity of the Shannon information and information energy in both position and momentum spaces. The complexity measure which is equivalent to Cramer–Rao uncertainty product is determined. We have obtained the information content stored, the concentration of quantum system and complexity measure numerically for n = 0, 1, 2 and 3 respectively.

  4. 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.

  5. 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

  6. Evaporative mass transfer behavior of a complex immiscible liquid.

    PubMed

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

    2008-09-01

    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.

  7. 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

  8. Evaporative mass transfer behavior of a complex immiscible liquid.

    PubMed

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

    2008-09-01

    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

  9. 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

  10. Teaching for Transfer: A Perspective. Information Series No. 141.

    ERIC Educational Resources Information Center

    Selz, Nina; Ashley, William L.

    Both the process and the antecedents of transfer (transfer of skill or knowledge from prior experiences to new ones) are considered by the authors, who suggest ways that teaching for transfer can be implemented. Three questions relating to transfer are considered: Is the capacity or ability to transfer attended to and developed in education and…

  11. Information transfer by exosomes: A new frontier in hematologic malignancies.

    PubMed

    Boyiadzis, Michael; Whiteside, Theresa L

    2015-09-01

    Exosomes are small (30-150 mm) vesicles secreted by all cell types and present in all body fluids. They are emerging as vehicles for delivery of membrane-tethered signaling molecules and membrane enclosed genes to target cells. Exosome-mediated information transfer allows for crosstalk of cells within the hematopoietic system and for interactions between hematopoietic cells and local or distant tissue cells. Exosomes carry physiological signals essential for health and participate in pathological processes, including malignant transformation. In hematologic malignancies, exosomes reprogram the bone marrow microenvironment, creating a niche for abnormal cells and favoring their expansion. The molecular and genetic mechanisms exosomes utilize to shuttle information between cells are currently being examined as are the potential roles exosomes play as biomarkers of disease or future therapeutic targets.

  12. Information transfer rate with serial and simultaneous visual display formats

    NASA Astrophysics Data System (ADS)

    Matin, Ethel; Boff, Kenneth R.

    1988-04-01

    Information communication rate for a conventional display with three spatially separated windows was compared with rate for a serial display in which data frames were presented sequentially in one window. For both methods, each frame contained a randomly selected digit with various amounts of additional display 'clutter.' Subjects recalled the digits in a prescribed order. Large rate differences were found, with faster serial communication for all levels of the clutter factors. However, the rate difference was most pronounced for highly cluttered displays. An explanation for the latter effect in terms of visual masking in the retinal periphery was supported by the results of a second experiment. The working hypothesis that serial displays can speed information transfer for automatic but not for controlled processing is discussed.

  13. Role of Agrobacterium virB genes in transfer of T complexes and RSF1010.

    PubMed

    Fullner, K J

    1998-01-01

    Nonpolar virB mutants of Agrobacterium tumefaciens were tested for RSF1010 mobilization and extracellular complementation. virB2 to virB11 were essential for transfer in both assays. virB1 was essential only for high frequency transfer of RSF1010 and VirE2. Coordinated transfer of a preassembled T complex is supported by these data and competition studies. PMID:9440537

  14. Ultrafast Charge Photogeneration in MEH-PPV Charge-Transfer Complexes

    NASA Astrophysics Data System (ADS)

    Bakulin, Artem A.; Paraschuk, Dmitry Yu.; Pshenichnikov, Maxim S.; van Loosdrecht, Paul H. M.

    Visible-pump-IR-probe spectroscopy is used to study the ultrafast charge dynamics in MEH-PPV based charge-transfer complexes and donor-acceptor blends. Transient anisotropy of the polymer polaron band provides invaluable insights into excitation localisation and charge-transfer pathways.

  15. 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.

  16. 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.

  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. 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)

  19. 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

  20. 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.

  1. 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

  2. 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

  3. 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.

  4. 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.

  5. 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...

  6. 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.

  7. Spectrophotometric and some thermodynamic parameters of the charge transfer complexation between chloranilic acid and chlorpheniramine.

    PubMed

    Ofoefule, S I; Ajali, U

    2001-01-01

    The principle of charge transfer complexation involving a pi-acceptor (chloranilic acid) and an n-donor (chlorpheniramine) was utilized in the assay of the later in its pure form and in its tablet dosage forms. Some thermodynamic parameters of the complex such as association constant (Kc), molar absorptivity (epsilon c), free energy change (delta G degree), enthalpy (delta H degree) and entropy (delta S degree) changes were determined to establish the stability of the complex and the optimum conditions for the complex formation. The values obtained for these thermodynamic parameters indicated that the complex formed between this two chemical entities is highly stable. Assay of chlorpheniramine in its pure form and in its tablet dosage forms gave high percentage recoveries. The principle of charge transfer complexation could therefore be employed in the colorimetric assay of chlorpheniramine in its tablet dosage forms.

  8. 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.

  9. Luminescent charge-transfer complexes: tuning emission in binary fluorophore mixtures.

    PubMed

    Gujrati, Maneesh D; Kumar, N S Saleesh; Brown, Adrienne S; Captain, Burjor; Wilson, James N

    2011-06-01

    Charge-transfer (CT) complexes composed of a π-electron-poor naphthalene diimide (NDI) derivative combined with a series of π-electron-rich donors were investigated. Solutions of the CT complexes are nonemissive; however, solid-state complexes and aqueous suspensions display emission that is dependent on the energy of the HOMO of the electron donor. Crystallographic analysis of a pyrene-NDI complex reveals columnar packing and a high degree of frontier molecular orbital (FMO) overlap that likely contributes to the observed optical properties. The fluorescent CT particles are utilized as imaging agents; additional luminescent CT complexes may be realized by considering FMO energies and topologies. PMID:21548624

  10. The origin and dynamic evolution of chemical information transfer.

    PubMed

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

    2011-04-01

    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.

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

    SciTech Connect

    Atwood, J.

    1990-01-01

    During the course of Grant ER13775 we have constructed an infrared stopped-flow spectrophotometer and initiated a study of the mechanisms of reactions that involve a change in the oxidation state of organometallic complexes. The spectrometer combined conventional stopped-flow techniques with an infrared optical system comprised of a carbon monoxide laser, an IRTRAN flow-through cell and a mercury-cadium-telluride detector. In this summary we will highlight our results on reactions: (1) that formally involve exchange of a charged species between two metal carbonyl anions, (2) that involve additional of an electron to, or removal of an electron from organometallic complexes that contain a metal-metal bond, and (3) between coordination complexes and metal carbonyl anions. 12 refs.

  12. Methods of information theory and algorithmic complexity for network biology.

    PubMed

    Zenil, Hector; Kiani, Narsis A; Tegnér, Jesper

    2016-03-01

    We survey and introduce concepts and tools located at the intersection of information theory and network biology. We show that Shannon's information entropy, compressibility and algorithmic complexity quantify different local and global aspects of synthetic and biological data. We show examples such as the emergence of giant components in Erdös-Rényi random graphs, and the recovery of topological properties from numerical kinetic properties simulating gene expression data. We provide exact theoretical calculations, numerical approximations and error estimations of entropy, algorithmic probability and Kolmogorov complexity for different types of graphs, characterizing their variant and invariant properties. We introduce formal definitions of complexity for both labeled and unlabeled graphs and prove that the Kolmogorov complexity of a labeled graph is a good approximation of its unlabeled Kolmogorov complexity and thus a robust definition of graph complexity.

  13. (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.

  14. [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.

  15. 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

  16. 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.

  17. Social complexity can drive vocal complexity: group size influences vocal information in Carolina chickadees.

    PubMed

    Freeberg, Todd M

    2006-07-01

    One hypothesis to explain variation in vocal communication in animal species is that the complexity of the social group influences the group's vocal complexity. This social-complexity hypothesis for communication is also central to recent arguments regarding the origins of human language, but experimental tests of the hypothesis are lacking. This study investigated whether group size, a fundamental component of social complexity, influences the complexity of a call functioning in the social organization of Carolina chickadees, Poecile carolinensis. In unmanipulated field settings, calls of individuals in larger groups had greater complexity (more information) than calls of individuals in smaller groups. In aviary settings manipulating group size, individuals in larger groups used calls with greater complexity than individuals in smaller groups. These results indicate that social complexity can influence communicative complexity in this species. PMID:16866738

  18. Recent aspects of the proton transfer reaction in H-bonded complexes

    NASA Astrophysics Data System (ADS)

    Szafran, Mirosław

    1996-07-01

    Proton transfer processes cover a very wide range of situations and time scales and they are of great interest from the viewpoint of chemical reactions in solution. These processes can occur via thermally activated crossing or tunneling. This review considers various aspects of this many-faceted field. Spectroscopic, dielectric, colligative and energetic properties and structures of various species with H-bonds are examined. Proton transfer reactions in water and organic solvents, and the contribution of various H-bonded species and ions to these processes are discussed. Among other topics, this survey includes the effects of solvent, acid-base stoichiometry, concentration, temperature and impurity on proton transfer reactions in complexes of phenols and carboxylic acids with amines, pyridines and pyridine N-oxides. The contribution of the nonstoichiometric acid-base complexes and ionic species to the reversible proton transfer mechanism is discussed.

  19. Acquisition of detailed heat transfer behavior in complex internal flow passages

    NASA Astrophysics Data System (ADS)

    Metzger, D. E.; Bunker, R. S.; Fan, C. S.

    Flow passages associated with internal cooling of high temperature engine components, especially those in gas turbine engines, frequently have very complex surface geometries. The flow channels usually are roughened to enhance heat transfer rates, and often incorporate sharp turns. The acquisition of detailed local heat transfer coefficient distributions over complex surface geometries is often extremely difficult or prohibitively expensive using conventional techniques. A relatively new method of acquiring heat transfer coefficients through use of surface coatings that have precise melting points is described. As an example of the use of the technique, it is applied to the study of the effect of various rib roughness patterns on heat transfer through 90 deg turns in a rectangular cooling channel.

  20. 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

  1. 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

  2. Charge-transfer luminescence from ruthenium(II) complexes containing tridentate ligands

    NASA Astrophysics Data System (ADS)

    Stone, M. L.; Crosby, G. A.

    Four complexes of the general formula Ru(NNN) 2+2 (N NN = tridentate N-heterocyclic ligand) were synthesized and studied spectroscopically. All exhibit visible absorption spectra that are charge-transfer-to-ligand in origin, are luminescent in glasses at 77 K, and display emission spectra that possess energies, structures, and decay tines that label them as charge transfer.

  3. 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…

  4. 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

  5. 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.

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

    PubMed Central

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

    2008-01-01

    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

  7. 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.

  8. 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

  9. Proton-coupled electron transfer and multielectron oxidations in complexes of ruthenium and osmium

    SciTech Connect

    Dovletoglou, A.

    1992-01-01

    This doctoral research concerns the mechanism of proton-coupled electron transfer over an extended pH range. These processes between ruthenium and osmium complexes and hydroquinones have been studied using spectrophotometric methods and cyclic voltammetry. Elucidation of the mechanistic details has been attempted by using isotopic labelling, kinetic analysis, and numerical simulation of complex kinetic schemes. The coordination and redox chemistry of polypyridyl-acetylacetonato and -oxalato complexes of ruthenium and the role of ancillary ligands in defining the properties of Ru[sup IV]O complexes were explored. These studies represent the first attempt to probe possible 2e[sup [minus

  10. Charge-transfer complexes of 4-nitrocatechol with some amino alcohols

    NASA Astrophysics Data System (ADS)

    Baniyaghoob, Sahar; Najafpour, Mohammad Mahdi; Boghaei, Davar M.

    2010-03-01

    Charge-transfer (CT) complexes formed from the reactions of 4-nitropyrocatechol (4-nCat) as an electron acceptor with four amino alcohols: 2-aminoethanol, 1-amino-2-propanol, 4-aminobutanol and N-(2-hydroxyethyl)-1,3-diaminopropane (NHEDAP) as electron donors, have been studied spectrophotometrically in H 2O and H 2O/EtOH at 20, 25, 30, 35 and 40 °C. The calculated values of the oscillator strength and transition moment confirm the formation of CT-complexes. The thermodynamic and spectroscopic parameters were also evaluated for the formation of CT-complexes. The equilibrium constants ranged from 9.00 to 2.20 l mol -1 (M -1). These interactions are exothermic and have relatively large standard enthalpy and entropy changes (Δ H values ranged from -15.58 to -3.10 kJ mol -1; Δ S ranged from 26.81 to -3.25 J K -1 mol -1). The solid CT-complexes have been synthesized and characterized by IR, NMR, mass spectrometry and thermal analysis. The photometric titration curves and other spectrometric data for the reactions indicated that the data obtained refer to the formation of 1:1 charge-transfer complex of [(4-nCat) (NHEDAP)] and 1:2 charge-transfer complexes of other amino alcohols [(4-nCat) (amino alcohol) 2]. The effect of alkali and alkaline earth metals on increasing the equilibrium constant of the CT-complexation was also investigated.

  11. 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.

  12. 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.

  13. Accessible information for people with complex communication needs.

    PubMed

    Owens, Janet S

    2006-09-01

    Information can be empowering if it is accessible. While a number of known information access barriers have been reported for the broader group of people with disabilities, specific information issues for people with complex communication needs have not been previously reported. In this consumer-focused study, the accessibility of information design and dissemination practices were discussed by 17 people with complex communication needs; by eight parents, advocates, therapists, and agency representatives in focus groups; and by seven individuals in individual interviews. Participants explored issues and made recommendations for content, including language, visual and audio supports; print accessibility; physical access; and human support for information access. Consumer-generated accessibility guidelines were an outcome of this study.

  14. 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

  15. 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

  16. 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

  17. The structure of an electron transfer complex containing a cytochrome c and a peroxidase.

    PubMed

    Pettigrew, G W; Prazeres, S; Costa, C; Palma, N; Krippahl, L; Moura, I; Moura, J J

    1999-04-16

    Efficient biological electron transfer may require a fluid association of redox partners. Two noncrystallographic methods (a new molecular docking program and 1H NMR spectroscopy) have been used to study the electron transfer complex formed between the cytochrome c peroxidase (CCP) of Paracoccus denitrificans and cytochromes c. For the natural redox partner, cytochrome c550, the results are consistent with a complex in which the heme of a single cytochrome lies above the exposed electron-transferring heme of the peroxidase. In contrast, two molecules of the nonphysiological but kinetically competent horse cytochrome bind between the two hemes of the peroxidase. These dramatically different patterns are consistent with a redox active surface on the peroxidase that may accommodate more than one cytochrome and allow lateral mobility. PMID:10196231

  18. Copper-homoscorpionate complexes as active catalysts for atom transfer radical addition to olefins.

    PubMed

    Muñoz-Molina, José María; Caballero, Ana; Díaz-Requejo, M Mar; Trofimenko, Swiatoslaw; Belderraín, Tomas R; Pérez, Pedro J

    2007-09-17

    Cu(I) complexes containing trispyrazolylborate ligands efficiently catalyze the atom transfer radical addition (ATRA) of polyhalogenated alkanes to various olefins under mild conditions. The catalytic activity is enhanced when bulky and electron donating Tpx ligands are employed. Kinetic data have allowed the proposal of a mechanistic interpretation that includes a Cu(II) pentacoordinated species that regulates the catalytic cycle.

  19. Efficient estimation of energy transfer efficiency in light-harvesting complexes.

    PubMed

    Shabani, A; Mohseni, M; Rabitz, H; Lloyd, S

    2012-07-01

    The fundamental physical mechanisms of energy transfer in photosynthetic complexes is not yet fully understood. In particular, the degree of efficiency or sensitivity of these systems for energy transfer is not known given their realistic with surrounding photonic and phononic environments. One major problem in studying light-harvesting complexes has been the lack of an efficient method for simulation of their dynamics in biological environments. To this end, here we revisit the second order time-convolution (TC2) master equation and examine its reliability beyond extreme Markovian and perturbative limits. In particular, we present a derivation of TC2 without making the usual weak system-bath coupling assumption. Using this equation, we explore the long-time behavior of exciton dynamics of Fenna-Matthews-Olson (FMO) portein complex. Moreover, we introduce a constructive error analysis to estimate the accuracy of TC2 equation in calculating energy transfer efficiency, exhibiting reliable performance for system-bath interactions with weak and intermediate memory and strength. Furthermore, we numerically show that energy transfer efficiency is optimal and robust for the FMO protein complex of green sulfur bacteria with respect to variations in reorganization energy and bath correlation time scales.

  20. 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

  1. Preparation of C{sub 60} charge transfer complexes with organic donor molecules and alkali doping

    SciTech Connect

    Otsuka, A.; Saito, G.; Hirate, S.; Pac, S.; Ishida, T.; Zakhidov, A.A.; Yakushi, K.

    1998-07-01

    Solid charge transfer (CT) complexes of C{sub 60} with TseC{sub 1}-TTF, EDT-TTF, EOET-TTF, and TDAP (1, 3, 6, 8-tetrakis(dimethylamino)pyrene) were newly prepared. All the obtained black crystals were proved to be neutral despite their rather strong electron donor ability. Lattice parameters of them except for EOET-TTF complex were determined together with those of HMTTeF{center_dot}C{sub 60}, which had been reported with different values. Rubidium doping under a mild condition was examined on the complexes of TDAP, EOET-TTF, HMTTeF, BEDT-TTF, hydroquinone and ferrocene to search for the superconductors of new crystal and electronic structures. Among them, the rubidium-doped ferrocene complex easily showed an apparent superconducting signal in SQUID magnetization measurements. The doping effect on these CT complexes is compared to that on OMTTF complex.

  2. 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

  3. 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.

  4. 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.

  5. 77 FR 71035 - Financial Management Service; Proposed Collection of Information: Electronic Funds Transfer (EFT...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-11-28

    ... Fiscal Service Financial Management Service; Proposed Collection of Information: Electronic Funds Transfer (EFT) Market Research Study AGENCY: Financial Management Service, Fiscal Service, Treasury. ACTION...: Direct all written comments to Financial Management Service, Records and Information Management...

  6. 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... Financial Management Service solicits comments on the collection of information described below:...

  7. 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.

  8. 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.

  9. 78 FR 59772 - Proposed Information Collection (Evidence for Transfer of Entitlement of Education Benefits...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2013-09-27

    ... AFFAIRS Proposed Information Collection (Evidence for Transfer of Entitlement of Education Benefits.... Title: Evidence for Transfer of Entitlement of Education Benefits (38 CFR 21.7080). OMB Control Number... information electronically as evidence that the servicemember was approved by the military to...

  10. 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...

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

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-06-16

    ... Regulation; Information Collection; Payment by Electronic Fund Transfer AGENCY: Department of Defense (DOD... transfer. Public comments are particularly invited on: Whether this collection of information is necessary... those who are to respond, through the use of appropriate technological collection techniques or...

  12. 25 CFR 43.19 - Transfer of information by third parties.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 25 Indians 1 2011-04-01 2011-04-01 false Transfer of information by third parties. 43.19 Section 43.19 Indians BUREAU OF INDIAN AFFAIRS, DEPARTMENT OF THE INTERIOR EDUCATION MAINTENANCE AND CONTROL OF STUDENT RECORDS IN BUREAU SCHOOLS § 43.19 Transfer of information by third parties....

  13. 25 CFR 43.19 - Transfer of information by third parties.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 25 Indians 1 2010-04-01 2010-04-01 false Transfer of information by third parties. 43.19 Section 43.19 Indians BUREAU OF INDIAN AFFAIRS, DEPARTMENT OF THE INTERIOR EDUCATION MAINTENANCE AND CONTROL OF STUDENT RECORDS IN BUREAU SCHOOLS § 43.19 Transfer of information by third parties....

  14. Scientific and Technical Information Transfer for Education (STITE). Research Report. Final Report.

    ERIC Educational Resources Information Center

    Zunde, Pranas

    Science education can be enhanced by facilitating student interactive access to scientific data bases. The main objective of the Science and Technology Information Transfer for Education (STITE) project was to study man-machine mechanisms for improving the transfer of science information from its present repositories into science learning systems,…

  15. 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

  16. Transfer of lexical information in adults with reading disorders.

    PubMed

    Walker, M M

    2001-08-01

    This study was designed to test whether adults with reading disorders differ from adults with normal reading abilities in their interhemispheric transfer rates during a lexical decision task. Correlations of performance were completed between lexical decision vocal reaction times (msec.), interhemispheric reaction rates (RVF vocal reaction times-LVF vocal reaction times) and measures of decoding skills, including sight word decoding and phonological decoding for 20 adults with reading disorders and 20 with normal reading abilities. Following a series of Pearson product-moment correlations, the correlation between interhemispheric transfer time and sightword recognition was significant and negative for the adults with reading disorders. This value indicates a significant association between the direction of the interhemispheric transfer time times and sight-word recognition for reading-disordered adults. When correlations were negative (LVF) reaction times < RVF reaction times), stronger sight-word recognition scores were found. The correlation between interhemispheric transfer time and sight-word recognition was not significant for the normal reading adults. For both groups, the correlations between interhemispheric transfer time and phonological decoding were not significant so an association between phonological decoding and interhemispheric transfer time was not evident, The current findings suggest a strong relationship between reading proficiency and reaction times in completing the lexical decision task for the reading-disordered adults.

  17. The Alternative complex III: properties and possible mechanisms for electron transfer and energy conservation.

    PubMed

    Refojo, Patrícia N; Teixeira, Miguel; Pereira, Manuela M

    2012-10-01

    Alternative complexes III (ACIII) are recently identified membrane-bound enzymes that replace functionally the cytochrome bc(1/)b(6)f complexes. In general, ACIII are composed of four transmembrane proteins and three peripheral subunits that contain iron-sulfur centers and C-type hemes. ACIII are built by a combination of modules present in different enzyme families, namely the complex iron-sulfur molybdenum containing enzymes. In this article a historical perspective on the investigation of ACIII is presented, followed by an overview of the present knowledge on these enzymes. Electron transfer pathways within the protein are discussed taking into account possible different locations (cytoplasmatic or periplasmatic) of the iron-sulfur containing protein and their contribution to energy conservation. In this way several hypotheses for energy conservation modes are raised including linear and bifurcating electron transfer pathways. This article is part of a Special Issue entitled: 17th European Bioenergetics Conference (EBEC 2012).

  18. 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.

  19. Dissemination of information in complex networks with congestion

    NASA Astrophysics Data System (ADS)

    Cholvi, Vicent

    2006-07-01

    We address the problem of message transfer in complex networks with congestion. We propose a new strategy aimed at improving routing efficiency. Such a strategy, contrary to the shortest available path length from a given source to its destination (perhaps the most widely analyzed routing strategy), takes into account the congestion of nodes and can be deployed, with a minimal overhead, on top of it. Our results show that, by distributing more homogeneously the congestion of nodes, it significantly reduces the average network load as well as the collapse point.

  20. Excitation-energy transfer dynamics of higher plant photosystem I light-harvesting complexes.

    PubMed

    Wientjes, Emilie; van Stokkum, Ivo H M; van Amerongen, Herbert; Croce, Roberta

    2011-03-01

    Photosystem I (PSI) plays a major role in the light reactions of photosynthesis. In higher plants, PSI is composed of a core complex and four outer antennas that are assembled as two dimers, Lhca1/4 and Lhca2/3. Time-resolved fluorescence measurements on the isolated dimers show very similar kinetics. The intermonomer transfer processes are resolved using target analysis. They occur at rates similar to those observed in transfer to the PSI core, suggesting competition between the two transfer pathways. It appears that each dimer is adopting various conformations that correspond to different lifetimes and emission spectra. A special feature of the Lhca complexes is the presence of an absorption band at low energy, originating from an excitonic state of a chlorophyll dimer, mixed with a charge-transfer state. These low-energy bands have high oscillator strengths and they are superradiant in both Lhca1/4 and Lhca2/3. This challenges the view that the low-energy charge-transfer state always functions as a quencher in plant Lhc's and it also challenges previous interpretations of PSI kinetics. The very similar properties of the low-energy states of both dimers indicate that the organization of the involved chlorophylls should also be similar, in disagreement with the available structural data.

  1. Spectroscopic studies on electron transfer between plastocyanin and cytochrome b6f complex.

    PubMed

    Sujak, A; Drepper, F; Haehnel, W

    2004-05-27

    This paper reports the results of the research on the interaction between the highly active cytochrome b(6)f complex and plastocyanin, both isolated from the same source - spinachia oleracea plants. An equilibrium constant K between the cytochrome f of the cytochrome b(6)f complex and plastocyanin has been estimated by two independent spectroscopic techniques: steady-state absorption spectroscopy and stopped-flow. The second-order rate constants k2 for forward and backward electron transfer between cytochrome f and plastocyanin have been found between 1.4-2 x 10(7) and 8-10 x 10(6) M(-1)s(-1), respectively, giving the value of an equilibrium constant of about 2+/-0.4 or a difference in redox potential between plastocyanin and cytochrome f of cytochrome b(6)f complex of ca. 17 mV. The value of K=1.7+/-0.3 has been estimated from steady-state experiments in which the initial and final concentrations of participating components after mixing have been estimated via differential spectra analysis or spectra deconvolution. We propose a method of evaluation of the final plastocyanin concentration after the electron transfer reaction between cytochrome bf complex and plastocyanin that overcomes the interference by the strong chlorophyll absorption in the spectral region where oxidised plastocyanin has its low extinction absorption band. The data from both experiments, in the system devoid of quinol being the electron donor to cytochrome b(6), suggest that in case of electron transfer from cytochrome f to plastocyanin electron transfer can either bypass cytochrome f or the Rieske iron-sulfur protein can be reduced prior to its movement to the quinol binding site of cytochrome b(6). The role of the Rieske protein in forward and backward electron transfer reactions is discussed.

  2. 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.

  3. Charge-transfer complexes of 4-nitrocatechol with some amino alcohols.

    PubMed

    Baniyaghoob, Sahar; Najafpour, Mohammad Mahdi; Boghaei, Davar M

    2010-03-01

    Charge-transfer (CT) complexes formed from the reactions of 4-nitropyrocatechol (4-nCat) as an electron acceptor with four amino alcohols: 2-aminoethanol, 1-amino-2-propanol, 4-aminobutanol and N-(2-hydroxyethyl)-1,3-diaminopropane (NHEDAP) as electron donors, have been studied spectrophotometrically in H(2)O and H(2)O/EtOH at 20, 25, 30, 35 and 40 degrees C. The calculated values of the oscillator strength and transition moment confirm the formation of CT-complexes. The thermodynamic and spectroscopic parameters were also evaluated for the formation of CT-complexes. The equilibrium constants ranged from 9.00 to 2.20 l mol(-1) (M(-1)). These interactions are exothermic and have relatively large standard enthalpy and entropy changes (DeltaH values ranged from -15.58 to -3.10 kJ mol(-1); DeltaS ranged from 26.81 to -3.25 J K(-1)mol(-1)). The solid CT-complexes have been synthesized and characterized by IR, NMR, mass spectrometry and thermal analysis. The photometric titration curves and other spectrometric data for the reactions indicated that the data obtained refer to the formation of 1:1 charge-transfer complex of [(4-nCat) (NHEDAP)] and 1:2 charge-transfer complexes of other amino alcohols [(4-nCat) (amino alcohol)(2)]. The effect of alkali and alkaline earth metals on increasing the equilibrium constant of the CT-complexation was also investigated.

  4. 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

  5. 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.

  6. Carotenoid-bacteriochlorophyll energy transfer in LH2 complexes studied with 10-fs time resolution.

    PubMed

    Polli, Dario; Cerullo, Giulio; Lanzani, Guglielmo; De Silvestri, Sandro; Hashimoto, Hideki; Cogdell, Richard J

    2006-04-01

    In this report, we present a study of carotenoid-bacteriochlorophyll energy transfer processes in two peripheral light-harvesting complexes (known as LH2) from purple bacteria. We use transient absorption spectroscopy with approximately 10 fs temporal resolution, which is necessary to observe the very fast energy relaxation processes. By comparing excited-state dynamics of the carotenoids in organic solvents and inside the LH2 complexes, it has been possible to directly evaluate their energy transfer efficiency to the bacteriochlorophylls. In the case of okenone in the LH2 complex from Chromatium purpuratum, we obtained an energy transfer efficiency of etaET2=63+/-2.5% from the optically active excited state (S2) and etaET1=61+/-2% from the optically dark state (S1); for rhodopin glucoside contained in the LH2 complex from Rhodopseudomonas acidophila these values become etaET2=49.5+/-3.5% and etaET1=5.1+/-1%. The measurements also enabled us to observe vibrational energy relaxation in the carotenoids' S1 state and real-time collective vibrational coherence initiated by the ultrashort pump pulses. Our results are important for understanding the dynamics of early events of photosynthesis and relating it to the structural arrangement of the chromophores.

  7. Sources and Information on the Scope and Impact of Reverse Transfers.

    ERIC Educational Resources Information Center

    LeBard, Christine M.

    1999-01-01

    Reviews documents submitted to the ERIC database over the past decade demonstrating the complexity of issues arising from diversification of the transfer-student population. Enumerates some primary concerns regarding reverse transfer students: defining the population, understanding its demographics, tracking student progress, responding to unique…

  8. 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…

  9. [Synthesis, spectroscopy and antibacterial activity of charge transfer complexes of heteropolytungstate containing sulfanilamide].

    PubMed

    Feng, Chang-Gen; Xiong, Yu-Di; Liu, Xia

    2010-06-01

    Two charge transfer complexes of heteropolytungstate with Keggin structure, (C6 H9 N2 O2S) 3PW12 O40 x 6H2O (SPW12) and (C6 H9 N2 O2S)4 SiW12 O40 x 5H2O (SSiW12) were synthesized with 12-tungstophosphoric (silicic) acid and sulfanilamide in aqueous phase. The title complexes were characterized by means of elementary analysis, FTIR, UV, 1H NMR, XRD and TG-DSC. The results indicate that the title complexes are new heteropoly compounds, and the UV results reveal that there is a charge transfer interaction between sulfanilamide and heteropoly anion. Thermal analysis shows that the process of mass loss of the title complexes is carried out in four stages, and the two complexes begin to decompose at 272.8 degrees C and 330.4 degrees C, respectively. The intermediates of the thermal decomposition were identified by FTIR Antibacterial test results show that the title complexes both have good antibacterial activity, and the inhibition rate of SPW12 to Escherichia coli, Staphylococcus aurous is 73.28% and 99.36%, respectively. PMID:20707125

  10. 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

  11. 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

  12. 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

  13. 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

  14. 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

  15. Role of protein fluctuation correlations in electron transfer in photosynthetic complexes.

    PubMed

    Nesterov, Alexander I; Berman, Gennady P

    2015-04-01

    We consider the dependence of the electron transfer in photosynthetic complexes on correlation properties of random fluctuations of the protein environment. The electron subsystem is modeled by a finite network of connected electron (exciton) sites. The fluctuations of the protein environment are modeled by random telegraph processes, which act either collectively (correlated) or independently (uncorrelated) on the electron sites. We derived an exact closed system of first-order linear differential equations with constant coefficients, for the average density matrix elements and for their first moments. Under some conditions, we obtained analytic expressions for the electron transfer rates and found the range of parameters for their applicability by comparing with the exact numerical simulations. We also compared the correlated and uncorrelated regimes and demonstrated numerically that the uncorrelated fluctuations of the protein environment can, under some conditions, either increase or decrease the electron transfer rates. PMID:25974522

  16. 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…

  17. Informational Complexity and Functional Activity of RNA Structures

    PubMed Central

    Carothers, James M.; Oestreich, Stephanie C.; Davis, Jonathan H.

    2004-01-01

    Very little is known about the distribution of functional DNA, RNA, and protein molecules in sequence space. The question of how the number and complexity of distinct solutions to a particular biochemical problem varies with activity is an important aspect of this general problem. Here we present a comparison of the structures and activities of eleven distinct GTP-binding RNAs (aptamers). By experimentally measuring the amount of information required to specify each optimal binding structure, we show that defining a structure capable of 10-fold tighter binding requires approximately 10 additional bits of information. This increase in information content is equivalent to specifying the identity of five additional nucleotide positions and corresponds to an ∼1000-fold decrease in abundance in a sample of random sequences. We observe a similar relationship between structural complexity and activity in a comparison of two catalytic RNAs (ribozyme ligases), raising the possibility of a general relationship between the complexity of RNA structures and their functional activity. Describing how information varies with activity in other heteropolymers, both biological and synthetic, may lead to an objective means of comparing their functional properties. This approach could be useful in predicting the functional utility of novel heteropolymers. PMID:15099096

  18. 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

  19. Spectral element-Fourier method for unsteady conjugate heat transfer in complex geometry flows

    NASA Astrophysics Data System (ADS)

    Amon, Cristina H.

    1995-04-01

    A spectral-element Fourier method (SEFM) is presented for the direct numerical simulation of forced convective heat transfer and conjugate conduction/convection in transitional internal flows in complex geometries. The SEFM is employed for the spatial discretization of the unsteady, incompressible, three-dimensional Navier-Stokes and energy equations. The resulting discrete equations are solved by a semi-implicit method in time treating explicitly the convection operator and implicitly the remaining pressure and viscous contributions. This methodology is illustrated by performing direct numerical simulations to investigate forced convective heat transfer in supercritical self-sustained oscillatory flows and conjugate effects in multimaterial domains. Highly unsteady flows in complex geometries are considered, including modified channels with periodic inhomogeneities such as spanwise rectangular and triangular grooves encountered in electronic equipment and compact heat exchangers.

  20. Fluorescence energy transfer between subfragment-1 and actin points in the rigor complex of actosubfragment-1.

    PubMed

    Takashi, R

    1979-11-13

    The fast-reacting thiol (SH1) of myosin subfragment-1 (S-1) was covalently and specifically labeled with (iodoacetamido)fluorescein (IAF), while Cys-373 of actin was also covalently and preferentially labeled with N-(iodoacetyl)-N'-(1-sulfo-5-naphthyl)ethylenediamine (1,5-IAEDANS). The method of fluorescence energy transfer was used to examine the spatial proximity between the two sites, i.e., SH1 and Cys-373, in the rigor complex of acto-S-1. Approximately 30% fluorescence energy transfer was observed from the 1,5-IAEDANS on actin as a donor to the IAF on S-1 as an acceptor in their rigor complex; under certain assumptions this corresponds to a distance of ca. 6.0 nm.

  1. 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.

  2. 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.

  3. Fluorescence Resonance Energy Transfer Microscopy for Measuring Chromatin Complex Structure and Dynamics.

    PubMed

    Cherubini, Alessandro; Zippo, Alessio

    2016-01-01

    The Polycomb group (PcG) proteins form regulatory complexes that modify the chromatin structure and silence their target genes. Recent works have found that the composition of Polycomb complexes is highly dynamic. Defining the different protein components of each complex is fundamental for better understanding their biological functions. Fluorescent resonance energy transfer (FRET) is a powerful tool to measure protein-protein interactions, in nanometer order and in their native cellular environment. Here we describe the preparation and execution of a typical FRET experiment using CFP-tagged protein as donor and YFP-tagged protein as acceptor. We further show that FRET can be used in a competition assay to measure binding affinities of different components of the same chromatin complex. PMID:27659982

  4. Spectroscopy of charge transfer complexes of four amino acids as organic two-dimensional conductors

    NASA Astrophysics Data System (ADS)

    Padhiyar, Ashvin; Patel, A. J.; Oza, A. T.

    2007-12-01

    It is found in this study that four amino acids, namely asparagine, arginine, histidine and glutamine form two-dimensional conducting systems which are charge transfer complexes (CTCs) with organic acceptors like TCNQ, TCNE, chloranil, DDQ, TNF and iodine. It is verified using optical absorption edges that these are 2d conductors like transition metal dichalcogenides obeying absorption functions different from 1d and 3d conductors. This 2d nature is related to the network of intermolecular H-bonding in these complexes, which leads to a global H-bonded network resulting in the absence of local deformation due to the relaxation of strain.

  5. Study of charge transfer complexes of menadione (vitamin K 3) with a series of anilines

    NASA Astrophysics Data System (ADS)

    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.

  6. 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.

  7. 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

  8. Ab inito study on triplet excitation energy transfer in photosynthetic light-harvesting complexes.

    PubMed

    You, Zhi-Qiang; Hsu, Chao-Ping

    2011-04-28

    We have studied the triplet energy transfer (TET) for photosynthetic light-harvesting complexes, the bacterial light-harvesting complex II (LH2) of Rhodospirillum molischianum and Rhodopseudomonas acidophila, and the peridinin-chlorophyll a protein (PCP) from Amphidinium carterae. The electronic coupling factor was calculated with the recently developed fragment spin difference scheme (You and Hsu, J. Chem. Phys. 2010, 133, 074105), which is a general computational scheme that yields the overall coupling under the Hamiltonian employed. The TET rates were estimated based on the couplings obtained. For all light-harvesting complexes studied, there exist nanosecond triplet energy transfer from the chlorophylls to the carotenoids. This result supports a direct triplet quenching mechanism for the photoprotection function of carotenoids. The TET rates are similar for a broad range of carotenoid triplet state energy, which implies a general and robust TET quenching role for carotenoids in photosynthesis. This result is also consistent with the weak dependence of TET kinetics on the type or the number of π conjugation lengths in the carotenoids and their analogues reported in the literature. We have also explored the possibility of forming triplet excitons in these complexes. In B850 of LH2 or the peridinin cluster in PCP, it is unlikely to have triplet exciton since the energy differences of any two neighboring molecules are likely to be much larger than their TET couplings. Our results provide theoretical limits to the possible photophysics in the light-harvesting complexes.

  9. 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.

  10. 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

  11. 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

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

    PubMed

    Pannwitz, Andrea; Wenger, Oliver S

    2016-04-28

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

  13. Structure and Electronic Spectra of Purine-Methyl Viologen Charge Transfer Complexes

    PubMed Central

    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 (MV) 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 1H 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 (TD) 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 GMP (DAD′DAD′ type) and 7-deazaguanosine zG (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

  14. 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.

  15. 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

  16. 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

  17. 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

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

    PubMed Central

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

    2013-01-01

    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

  19. Study of charge transfer complexes of [70]fullerene with phenol and substituted phenols.

    PubMed

    Bhattacharya, Sumanta; Banerjee, Shrabanti; Banerjee, Manas

    2005-07-01

    To improve the understanding of the charge transfer (CT) interaction of [70]fullerene with electron donors, interaction of [70]fullerene with a series of phenols, e.g., phenol, resorcinol and p-quinol were studied in 1,4-dioxan medium using absorption spectroscopy. An absorption band due to CT transition was observed in the visible region. The experimental CT transition energies (h nuCT) are well correlated (through Mulliken's equation) with the vertical ionisation potentials (I(D)v) of the series of phenols studied. From an analysis of this correlation degrees of charge transfer for the [70]fullerene-phenol complexes were estimated. The degrees of charge transfer in the ground state of the complexes have been found to be very low (<2%). The h nuCT values change systematically as the number and position of the -OH groups change on the aromatic ring of the phenol moiety. From the trends in the h nuCT values, the Hückel parameters (h(O) and k(C-O)) for the -OH group were obtained in a straightforward way and the values so obtained, viz., 1.91 and 1.0, respectively, are close to the ones (1.8 and 0.8) recommended by Streitwieser on the basis of other evidence. Oscillator strengths, transition dipole strengths and resonance energies of the [70]fullerene-phenol complexes were determined. Formation constants of the CT complexes were determined at four different temperatures from which enthalpies and entropies of formation of the complexes were estimated.

  20. Geometry and quadratic nonlinearity of charge transfer complexes in solution: a theoretical study.

    PubMed

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

    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, β(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.

  1. 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.

  2. 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…

  3. 75 FR 68035 - Proposed Information Collection (Evidence for Transfer of Entitlement of Education Benefits...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-11-04

    ... AFFAIRS Proposed Information Collection (Evidence for Transfer of Entitlement of Education Benefits.... Title: Evidence for Transfer of Entitlement of Education Benefits (38 CFR 21.7080). OMB Control Number... will accept DOD Form 2366-1 as evidence that the servicemember was approved by the military to...

  4. 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…

  5. A rigorous formalism of information transfer between dynamical system components. I. Discrete mapping

    NASA Astrophysics Data System (ADS)

    Liang, X. San; Kleeman, Richard

    2007-07-01

    We put the concept of information transfer on a rigorous footing and establish for it a formalism within the framework of discrete maps. The resulting transfer measure possesses a property of directionality or transfer asymmetry as emphasized by Schreiber [T. Schreiber, Measuring information transfer, Phys. Rev. Lett. 85 (2) (2000) 461]; it also verifies the transfer measure for two-dimensional systems, which was obtained by Liang and Kleeman [X.S. Liang, R. Kleeman, Information transfer between dynamical system components, Phys. Rev. Lett. 95 (24) (2005) 244101] through a different avenue. Connections to classical formalisms are explored and applications presented. We find that, in the context of the baker transformation, there is always information flowing from the stretching direction to the folding direction, while no transfer occurs in the opposite direction; we also find that, within the Hénon map system, the transfer from the quadratic component to the linear component is of a simple form as expected on physical grounds. This latter result is unique to our formalism.

  6. 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.

  7. Ferrocene-o-benzosemiquinonato tin(IV) electron-transfer complexes.

    PubMed

    Ilyakina, Ekaterina V; Poddel'sky, Andrey I; Fukin, Georgy K; Bogomyakov, Artem S; Cherkasov, Vladimir K; Abakumov, Gleb A

    2013-05-01

    The interaction of ferrocene with tin(IV) o-benzosemiquinonato complexes in acetonitrile results in a reversible electron transfer (ET) from ferrocene to the redox-active ligand with the formation of electron-transfer complexes [(3,6-Cat)SnBr3](-)[Cp2Fe](+) (1) and [(3,6-Cat)(3,6-SQ)SnCl2](-)[Cp2Fe](+) (2), where 3,6-Cat is the 3,6-di-tert-butyl-catecholate dianion and 3,6-SQ is the 3,6-di-tert-butyl-o-benzosemiquinonato radical anion. The ET process and the solvent effect in the system "ferrocene-o-benzosemiquinonato tin(IV) complexes" were investigated on the basis of a combination of spectroscopic and X-ray diffraction methods. The molecular structures of 1 and 2 were confirmed by X-ray analysis. Complex 2 demonstrates the ferromagnetic coupling in the linear chain alternating ···D(+•)A(-•)D(+•)A(-•)··· motif.

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. Bayesian Case-deletion Model Complexity and Information Criterion

    PubMed Central

    Zhu, Hongtu; Ibrahim, Joseph G.; Chen, Qingxia

    2015-01-01

    We establish a connection between Bayesian case influence measures for assessing the influence of individual observations and Bayesian predictive methods for evaluating the predictive performance of a model and comparing different models fitted to the same dataset. Based on such a connection, we formally propose a new set of Bayesian case-deletion model complexity (BCMC) measures for quantifying the effective number of parameters in a given statistical model. Its properties in linear models are explored. Adding some functions of BCMC to a conditional deviance function leads to a Bayesian case-deletion information criterion (BCIC) for comparing models. We systematically investigate some properties of BCIC and its connection with other information criteria, such as the Deviance Information Criterion (DIC). We illustrate the proposed methodology on linear mixed models with simulations and a real data example. PMID:26180578

  13. Selective growth of dual-color-emitting heterogeneous microdumbbells composed of organic charge-transfer complexes.

    PubMed

    Lei, Yi Long; Liao, Liang Sheng; Lee, Shuit Tong

    2013-03-13

    We report a simple yet versatile solution route for constructing heterojunctions from luminescent organic charge-transfer (CT) complexes through a two-step seeded-growth method. Using this method, we achieved anisotropic and selective growth of anthracene-1,2,4,5-tetracyanobenzene (TCNB) complexes onto the tips of naphthalene-TCNB microtubes, resulting in the formation of microdumbbells. Significantly, the two-component microdumbbells appear as dual-color-emitting heterojunctions arising from integration of two distinct color-emitting materials. We further elucidated the two-step seeded-growth mechanism of the dumbbell-like organic heterostructures on the basis of structural analysis of the two crystals and surface-interface energy balance. In principle, the present synthetic route may be used to fabricate a wide range of sophisticated dual- or multicolor-emitting organic heterostructures via judicious choice of the CT complexes.

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

    SciTech Connect

    Lippmann, M.J.; Antunez, E.

    1996-01-01

    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.

  15. 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.

  16. 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

  17. 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

  18. 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

  19. 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.

  20. 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

  1. 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.

  2. 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

  3. Transfer of Timing Information from RGC to LGN Spike Trains

    NASA Astrophysics Data System (ADS)

    Teich, Malvin C.; Lowen, Steven B.; Saleh, Bahaa E. A.; Kaplan, Ehud

    1998-03-01

    We have studied the firing patterns of retinal ganglion cells (RGCs) and their target lateral geniculate nucleus (LGN) cells. We find that clusters of spikes in the RGC neural firing pattern appear at the LGN output essentially unchanged, while isolated RGC firing events are more likely to be eliminated; thus the LGN action-potential sequence is therefore not merely a randomly deleted version of the RGC spike train. Employing information-theoretic techniques we developed for point processes,(B. E. A. Saleh and M. C. Teich, Phys. Rev. Lett.) 58, 2656--2659 (1987). we are able to estimate the information efficiency of the LGN neuronal output --- the proportion of the variation in the LGN firing pattern that carries information about its associated RGC input. A suitably modified integrate-and-fire neural model reproduces both the enhanced clustering in the LGN data (which accounts for the increased coefficient of variation) and the measured value of information efficiency, as well as mimicking the results of other observed statistical measures. Reliable information transmission therefore coexists with fractal fluctuations, which appear in RGC and LGN firing patterns.(M. C. Teich, C. Heneghan, S. B. Lowen, T. Ozaki, and E. Kaplan, J. Opt. Soc. Am. A) 14, 529--546 (1997).

  4. 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

  5. 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

  6. Method and apparatus for transfer function simulator for testing complex systems

    NASA Technical Reports Server (NTRS)

    Kavaya, M. J. (Inventor)

    1985-01-01

    A method and apparatus for testing the operation of a complex stabilization circuit in a closed loop system is presented. The method is comprised of a programmed analog or digital computing system for implementing the transfer function of a load thereby providing a predictable load. The digital computing system employs a table stored in a microprocessor in which precomputed values of the load transfer function are stored for values of input signal from the stabilization circuit over the range of interest. This technique may be used not only for isolating faults in the stabilization circuit, but also for analyzing a fault in a faulty load by so varying parameters of the computing system as to simulate operation of the actual load with the fault.

  7. 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.

  8. Quantum-information processing in disordered and complex quantum systems

    SciTech Connect

    Sen, Aditi; Sen, Ujjwal; Ahufinger, Veronica; Briegel, Hans J.; Sanpera, Anna; Lewenstein, Maciej

    2006-12-15

    We study quantum information processing in complex disordered many body systems that can be implemented by using lattices of ultracold atomic gases and trapped ions. We demonstrate, first in the short range case, the generation of entanglement and the local realization of quantum gates in a disordered magnetic model describing a quantum spin glass. We show that in this case it is possible to achieve fidelities of quantum gates higher than in the classical case. Complex systems with long range interactions, such as ions chains or dipolar atomic gases, can be used to model neural network Hamiltonians. For such systems, where both long range interactions and disorder appear, it is possible to generate long range bipartite entanglement. We provide an efficient analytical method to calculate the time evolution of a given initial state, which in turn allows us to calculate its quantum correlations.

  9. Analyzing complex networks evolution through Information Theory quantifiers

    NASA Astrophysics Data System (ADS)

    Carpi, Laura C.; Rosso, Osvaldo A.; Saco, Patricia M.; Ravetti, Martín Gómez

    2011-01-01

    A methodology to analyze dynamical changes in complex networks based on Information Theory quantifiers is proposed. The square root of the Jensen-Shannon divergence, a measure of dissimilarity between two probability distributions, and the MPR Statistical Complexity are used to quantify states in the network evolution process. Three cases are analyzed, the Watts-Strogatz model, a gene network during the progression of Alzheimer's disease and a climate network for the Tropical Pacific region to study the El Niño/Southern Oscillation (ENSO) dynamic. We find that the proposed quantifiers are able not only to capture changes in the dynamics of the processes but also to quantify and compare states in their evolution.

  10. Ligand-ligand charge-transfer excited states of Os(II) complexes

    SciTech Connect

    Perkins, T.A.; Schanze, K.S. ); Pourreau, D.B.; Netzel, T.L. )

    1989-06-01

    This paper examines the photophysics of metal-to-ligand charge-transfer (MLCT) and ligand-to-ligand charge-transfer (LLCT) excited states in a series of ((bpy){sub 2}Os{sup II}(CO)L){sup 2+} (Os-L) complexes. For each of the complexes studied, the d{pi}(Os) {yields} {pi}*(bpy) absorption band is the lowest energy transition that is apparent. For L = pyridine and benzonitrile, only long-lived, highly luminescent MLCT states are observed. However, when L = an electron-donor aminobenzonitrile (ABN) species (DMABN, TMABN, or CMI; see text), MLCT emission is quenched and in < 30 ps LLCT excited states are formed, *((bpy{sup {sm bullet}{minus}})-(bpy)OS{sup II}(CO)ABN{sup {sm bullet}+}){sup 2+}. The observed, weight-average radiationless decays of the LLCT excited states in acetonitrile and dichloromethane follow the squence Os-DMABN < Os-TMABN < Os-CMI in each solvent, and the calculated energies of the LLCT states for these complexes are in inverse order to the decay rates as expected if an energy gap law is followed. Finally, multiexponential relaxations of the LLCT states are pronounced in the nonpolar solvent dichloromethane. The dependence of these relaxations on the concentration of added electrolyte suggests that they may be due to ion-pair structure and dynamics.

  11. Long-Lived Charge Transfer Excited States in HBC-Polypyridyl Complex Hybrids.

    PubMed

    Elliott, Anastasia B S; Horvath, Raphael; Sun, Xue-Zhong; Gardiner, Michael G; Müllen, Klaus; Lucas, Nigel T; George, Michael W; Gordon, Keith C

    2016-05-16

    The synthesis of two bipyridine-hexa-peri-hexabenzocoronene (bpy-HBC) ligands functionalized with either (t)Bu or C12H25 and their Re(I) tricarbonyl chloride complexes are reported and their electronic properties investigated using spectroscopic and computational methods. The metal complexes show unusual properties, and we observed the formation of a long-lived excited state using time-resolved infrared spectroscopy. Depending on the solvent, this appears to be of the form Rebpy(•-)HBC(•+) or a bpy-centered π,π* state. TD-DFT calculations support the donor-acceptor charge transfer character of these systems, in which HBC is the donor and bpy is the acceptor. The ground state optical properties are dominated by the HBC chromophore with additional distinct transitions of the complexes, one associated with MLCT 450 nm (ε > 17 000 L mol(-1) cm(-1)) and another with a HBC/metal to bpy charge transfer, termed the MLLCT band (373 nm, ε = 66 000 L mol(-1) cm(-1)). These assignments are also supported by resonance Raman spectroscopy. PMID:27119791

  12. [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

  13. Ultrafast dynamics of Förster resonance energy transfer and photo-induced charge transfer in cationic polyfluorene/dye-labeled DNA complex.

    PubMed

    Kyhm, Kwangseuk; Kim, Inhong; Kang, Mijeong; Woo, Han Young

    2012-10-01

    The ultrafast dynamics of Förster resonance energy transfer (FRET) and photo-induced charge transfer (PCT) has been investigated in an electrostatic complex of a fluorescein-labeled single-stranded DNA (as a FRET acceptor) and a cationic polyfluorene copolymer (as a FRET donor). The donor-acceptor intermolecular distance and total energy transfer efficiency are determined for a polymer/DNA complex with two different counter-ions and compared with those obtained using a theoretical model by considering the competition between FRET and PCT processes. The maximum total energy transfer efficiency (0.47) was estimated at the optimum donor-acceptor intermolecular distance of 39.6 A.

  14. Minimal Model of Quantum Kinetic Clusters for the Energy-Transfer Network of a Light-Harvesting Protein Complex.

    PubMed

    Wu, Jianlan; Tang, Zhoufei; Gong, Zhihao; Cao, Jianshu; Mukamel, Shaul

    2015-04-01

    The energy absorbed in a light-harvesting protein complex is often transferred collectively through aggregated chromophore clusters. For population evolution of chromophores, the time-integrated effective rate matrix allows us to construct quantum kinetic clusters quantitatively and determine the reduced cluster-cluster transfer rates systematically, thus defining a minimal model of energy-transfer kinetics. For Fenna-Matthews-Olson (FMO) and light-havrvesting complex II (LCHII) monomers, quantum Markovian kinetics of clusters can accurately reproduce the overall energy-transfer process in the long-time scale. The dominant energy-transfer pathways are identified in the picture of aggregated clusters. The chromophores distributed extensively in various clusters can assist a fast and long-range energy transfer.

  15. 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.

  16. 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.

  17. Kinetics of the Dynamical Information Shannon Entropy for Complex Systems

    NASA Astrophysics Data System (ADS)

    Yulmetyev, R. M.; Yulmetyeva, D. G.

    1999-08-01

    Kinetic behaviour of dynamical information Shannon entropy is discussed for complex systems: physical systems with non-Markovian property and memory in correlation approximation, and biological and physiological systems with sequences of the Markovian and non-Markovian random noises. For the stochastic processes, a description of the information entropy in terms of normalized time correlation functions is given. The influence and important role of two mutually dependent channels of the entropy change, correlation (creation or generation of correlations) and anti-correlation (decay or annihilation of correlation) is discussed. The method developed here is also used in analysis of the density fluctuations in liquid cesium obtained from slow neutron scattering data, fractal kinetics of the long-range fluctuation in the short-time human memory and chaotic dynamics of R-R intervals of human ECG.

  18. Charge-transfer complexation as a general phenomenon in the copigmentation of anthocyanins.

    PubMed

    Ferreira da Silva, Palmira; Lima, João C; Freitas, Adilson A; Shimizu, Karina; Maçanita, Antonio L; Quina, Frank H

    2005-08-18

    Color intensification of anthocyanin solutions in the presence of natural polyphenols (copigmentation) is re-interpreted in terms of charge transfer from the copigment to the anthocyanin. Flavylium cations are shown to be excellent electron acceptors (E(red) approximately -0.3 V vs SCE). It is also demonstrated, for a large series of anthocyanin-copigment pairs, that the standard Gibbs free energy of complex formation decreases linearly with EA(Anthoc) - IP(Cop), the difference between the electron affinity of the anthocyanin, EA(Anthoc), and the ionization potential of the copigment, IP(Cop). Based on this correlation, copigmentation strengths of potential candidates for copigments can be predicted.

  19. 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.

  20. Potential Energy Surfaces and Charge Transfer of PAH-Sodium-PAH Complexes.

    PubMed

    Hjertenaes, Eirik; Andersson, Stefan; Koch, Henrik

    2016-09-19

    To further understanding of the role of sodium in carbon cathode degradation in Hall-Héroult cells, potential-energy surfaces and charge-transfer curves are presented for finite-size complexes of sodium intercalated between various polycyclic aromatic hydrocarbons. Calculations for lithium and potassium are included to highlight the disparate intercalation behaviour of the alkali metals in graphite intercalation compounds. Static energy barriers from DFT are used to compute macroscopic diffusion coefficients according to transition-state theory. Comparing the calculated diffusion coefficient to experimental values from the literature sheds light on the role of lattice diffusion of sodium-graphite intercalation compounds in sodium intrusion in graphitic carbon cathodes.

  1. Polaron hopping in some biomolecular solids and their charge transfer complexes.

    PubMed

    Solanki, G K; Amin, Anand; Padhiyar, Ashvin; Ray, A K; Oza, A T

    2008-12-01

    The solid state spectroscopy of charge transfer complexes of biomolecules such as fatty acids, tripalmitin, lysozyme. folic acid, beta-carotene, cytochrome c, valinomycin and gramicidin has been carried out. The absorption coefficient is related with electronic conductivity. A half-power beta density is found common among these macromolecular solids, indicating photon-induced polaron hopping or hopping of a charge carrier between two branches of a polariton. Band gap vs full width at half-maximum of the mid-IR peak also reveals a linear relation.

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. Electronic absorption spectra of charge-transfer complexes based on ferrocene and polyhalohydrocarbons

    SciTech Connect

    Germanova, L.F.; Balabanova, L.V.; Kochetkova, N.S.; Nelyubin, B.V.; Shuekhgeimer, M.G.; Vasil'eva, T.T.

    1986-01-10

    Polyhalomethanes, being as a rule strong electron acceptors, can play the role of photosensitizers of various classes of compounds including organometallic donors such as ferrocene, benchrotrene, etc. The authors found that polyhalohydrocarbons containing CHHal/sub 2/ and CHal/sub 3/ groups from with ferrocene charge-transfer complexes (CTC). Polyhalomethanes and polyhalo-2-pentenes show the highest activity in the reaction of complex formation with ferrocene. The compounds with the CBr/sub 3/ group in CTC have the highest extinction. An elongation of the alkyl chain in the molecule of polyhalogen derivatives and the presence of an additional halogen atom in the gamma position with respect to the CHal/sub 3/ group do not exert any significant influence on their CTC spectra with ferrocene.

  7. 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.

  8. 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.

  9. 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].

  10. Scientific and Technical Information Transfer for Education (STITE). Research Report No. 4.

    ERIC Educational Resources Information Center

    Zunde, Pranas

    Emphasizing the design of a data base management system for the experimental STITE (Scientific and Technical Information Transfer for Education) project, this progress report details the emerging features of this projected facility. Compiled by four STITE researchers, the report examines: science information communication, learning, dissemination,…

  11. Students Seeking Access to Four-Year Institutions: Community College Transfers [Background Information].

    ERIC Educational Resources Information Center

    Moore, Jamillah

    This publication provides background information for a hearing by the California Senate Select Committee on Higher Education and Outreach on December 3, 1997. The Introduction presents the Committee announcement, press release, agenda, information about transfer efforts in California, facts and figures about the community colleges, and the text of…

  12. 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.

  13. Information transfer through stochastic transmission of a linear combination of rates.

    PubMed

    Smyrnakis, Ioannis; Smirnakis, Stelios

    2013-09-01

    In this work, the Shannon information transfer rate due to the transmission of a linear combination of the firing rates of a number of afferent neurons is examined. The transmission of this linear combination (transfer statistic) takes place through a stochastic firing process, while a rate code is assumed. Constraints are imposed on the transmission process by the requirement that the coefficient of variation for the transfer statistic is small and by the relative variance of the individual terms in the calculation of the statistic. In the regime of no noise or signal correlations among the input neurons, simulations suggest that information transfer for fixed overall input is favored when there are few high-firing neurons, as opposed to more lower-firing neurons. Signal correlations among low-firing neurons can result in aggregates of high firing rates, improving in this way information transfer and calculational robustness. Under reasonable rate code assumptions, information transfer rates obtained are of the order 3 to 10 bit/sec.

  14. Decreasing Interferences and Time Spent on Transferring Information on Changing Nursing Shifts.

    PubMed

    Sans Torres, Elisenda; Albaladejo, Jessica Rubio; Benítez, Manuela

    2016-01-01

    The exchange of clinical information on patients is a common component in nursing shift changes where professionals have limited time to transfer this information. There is no standardized or structured methodology for transferring information, which requires increased time to complete. Also, during the exchange, some interruptions can disrupt the communication among professionals, which can affect the patient's safety. A descriptive study was developed for five months, the information transfer arrangement among nurses was changed in order to determine which interruption increased the time spent on shift change and, therefore, decreased the safety of pediatric patients. The results obtained on the type of interruption caused us to rethink the organization that includes pediatric patient care.

  15. Structural Information Inference from Lanthanoid Complexing Systems: Photoluminescence Studies on Isolated Ions

    NASA Astrophysics Data System (ADS)

    Greisch, Jean Francois; Harding, Michael E.; Chmela, Jiri; Klopper, Willem M.; Schooss, Detlef; Kappes, Manfred M.

    2016-06-01

    The application of lanthanoid complexes ranges from photovoltaics and light-emitting diodes to quantum memories and biological assays. Rationalization of their design requires a thorough understanding of intramolecular processes such as energy transfer, charge transfer, and non-radiative decay involving their subunits. Characterization of the excited states of such complexes considerably benefits from mass spectrometric methods since the associated optical transitions and processes are strongly affected by stoichiometry, symmetry, and overall charge state. We report herein spectroscopic measurements on ensembles of ions trapped in the gas phase and soft-landed in neon matrices. Their interpretation is considerably facilitated by direct comparison with computations. The combination of energy- and time-resolved measurements on isolated species with density functional as well as ligand-field and Franck-Condon computations enables us to infer structural as well as dynamical information about the species studied. The approach is first illustrated for sets of model lanthanoid complexes whose structure and electronic properties are systematically varied via the substitution of one component (lanthanoid or alkali,alkali-earth ion): (i) systematic dependence of ligand-centered phosphorescence on the lanthanoid(III) promotion energy and its impact on sensitization, and (ii) structural changes induced by the substitution of alkali or alkali-earth ions in relation with structures inferred using ion mobility spectroscopy. The temperature dependence of sensitization is briefly discussed. The focus is then shifted to measurements involving europium complexes with doxycycline an antibiotic of the tetracycline family. Besides discussing the complexes' structural and electronic features, we report on their use to monitor enzymatic processes involving hydrogen peroxide or biologically relevant molecules such as adenosine triphosphate (ATP).

  16. Charge Transfer Dissociation of Complex Oligosaccharides: Comparison with Collision-Induced Dissociation and Extreme Ultraviolet Dissociative Photoionization

    NASA Astrophysics Data System (ADS)

    Ropartz, David; Li, Pengfei; Fanuel, Mathieu; Giuliani, Alexandre; Rogniaux, Hélène; Jackson, Glen P.

    2016-08-01

    The structural characterization of oligosaccharides still challenges the field of analytical chemistry. Tandem mass spectrometry offers many advantages toward this aim, although the generic fragmentation method (low-energy collision-induced dissociation) shows clear limitations and is often insufficient to retrieve some essential structural information on these molecules. In this work, we present the first application of helium charge transfer dissociation (He-CTD) to characterize the structure of complex oligosaccharides. We compare this method with low-energy collision-induced dissociation and extreme-ultraviolet dissociative photoionization (XUV-DPI), which was shown previously to ensure the successful characterization of complex glycans. Similarly to what could be obtained by XUV-DPI, He-CTD provides a complete description of the investigated structures by producing many informative cross-ring fragments and no ambiguous fragmentation. Unlike XUV-DPI, which is performed at a synchrotron source, He-CTD has the undeniable advantage of being implementable in a conventional benchtop ion trap in a conventional laboratory setting.

  17. Charge Transfer Dissociation of Complex Oligosaccharides: Comparison with Collision-Induced Dissociation and Extreme Ultraviolet Dissociative Photoionization.

    PubMed

    Ropartz, David; Li, Pengfei; Fanuel, Mathieu; Giuliani, Alexandre; Rogniaux, Hélène; Jackson, Glen P

    2016-10-01

    The structural characterization of oligosaccharides still challenges the field of analytical chemistry. Tandem mass spectrometry offers many advantages toward this aim, although the generic fragmentation method (low-energy collision-induced dissociation) shows clear limitations and is often insufficient to retrieve some essential structural information on these molecules. In this work, we present the first application of helium charge transfer dissociation (He-CTD) to characterize the structure of complex oligosaccharides. We compare this method with low-energy collision-induced dissociation and extreme-ultraviolet dissociative photoionization (XUV-DPI), which was shown previously to ensure the successful characterization of complex glycans. Similarly to what could be obtained by XUV-DPI, He-CTD provides a complete description of the investigated structures by producing many informative cross-ring fragments and no ambiguous fragmentation. Unlike XUV-DPI, which is performed at a synchrotron source, He-CTD has the undeniable advantage of being implementable in a conventional benchtop ion trap in a conventional laboratory setting. Graphical Abstract ᅟ. PMID:27582116

  18. Charge Transfer Dissociation of Complex Oligosaccharides: Comparison with Collision-Induced Dissociation and Extreme Ultraviolet Dissociative Photoionization

    NASA Astrophysics Data System (ADS)

    Ropartz, David; Li, Pengfei; Fanuel, Mathieu; Giuliani, Alexandre; Rogniaux, Hélène; Jackson, Glen P.

    2016-10-01

    The structural characterization of oligosaccharides still challenges the field of analytical chemistry. Tandem mass spectrometry offers many advantages toward this aim, although the generic fragmentation method (low-energy collision-induced dissociation) shows clear limitations and is often insufficient to retrieve some essential structural information on these molecules. In this work, we present the first application of helium charge transfer dissociation (He-CTD) to characterize the structure of complex oligosaccharides. We compare this method with low-energy collision-induced dissociation and extreme-ultraviolet dissociative photoionization (XUV-DPI), which was shown previously to ensure the successful characterization of complex glycans. Similarly to what could be obtained by XUV-DPI, He-CTD provides a complete description of the investigated structures by producing many informative cross-ring fragments and no ambiguous fragmentation. Unlike XUV-DPI, which is performed at a synchrotron source, He-CTD has the undeniable advantage of being implementable in a conventional benchtop ion trap in a conventional laboratory setting.

  19. 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

  20. Determining protein complex structures based on a Bayesian model of in vivo Förster resonance energy transfer (FRET) data.

    PubMed

    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

    2014-11-01

    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.

  1. 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

  2. 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.

  3. 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.

  4. 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.

  5. Interligand electron transfer in heteroleptic ruthenium(II) complexes occurs on multiple time scales.

    PubMed

    Stark, Charles W; Schreier, Wolfgang J; Lucon, Janice; Edwards, Ethan; Douglas, Trevor; Kohler, Bern

    2015-05-21

    The time-dependent localization of the metal-to-ligand charge transfer (MLCT) excited states of ruthenium(II) complexes containing 2,2'-bipyridine (bpy) and 1,10-phenanthroline (phen) ligands was studied by femtosecond transient absorption spectroscopy. Time-resolved anisotropy measurements indicate that the excited state hops randomly among the three ligands of each complex by subpicosecond interligand electron transfer (ILET). Although the bpy- and phen-localized (3)MLCT states have similar energies and steady-state emission spectra, pronounced differences in their excited-state absorption spectra make it possible to observe changes in excited state populations using magic angle transient absorption measurements. Analysis of the magic angle signals shows that the excited electron is equally likely to be found on any of the three ligands approximately 1 ps after excitation, but this statistical distribution subsequently evolves to a Boltzmann distribution with a time constant of approximately 10 ps. The apparent contradiction between ultrafast ILET revealed by time-dependent anisotropy measurements and the slower ILET seen in magic angle measurements on the tens of picoseconds time scale is explained by a model in which the underlying rates depend dynamically on excess vibrational energy. The insight that ILET can occur over multiple time scales reconciles contradictory literature observations and may lead to improved photosensitizer performance.

  6. 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.

  7. 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

  8. 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.

  9. Structural and mutational studies of an electron transfer complex of maize sulfite reductase and ferredoxin.

    PubMed

    Kim, Ju Yaen; Nakayama, Masato; Toyota, Hiroshi; Kurisu, Genji; Hase, Toshiharu

    2016-08-01

    The structure of the complex of maize sulfite reductase (SiR) and ferredoxin (Fd) has been determined by X-ray crystallography. Co-crystals of the two proteins prepared under different conditions were subjected to the diffraction analysis and three possible structures of the complex were solved. Although topological relationship of SiR and Fd varied in each of the structures, two characteristics common to all structures were found in the pattern of protein-protein interactions and positional arrangements of redox centres; (i) a few negative residues of Fd contact with a narrow area of SiR with positive electrostatic surface potential and (ii) [2Fe-2S] cluster of Fd and [4Fe-4S] cluster of SiR are in a close proximity with the shortest distance around 12 Å. Mutational analysis of a total of seven basic residues of SiR distributed widely at the interface of the complex showed their importance for supporting an efficient Fd-dependent activity and a strong physical binding to Fd. These combined results suggest that the productive electron transfer complex of SiR and Fd could be formed through multiple processes of the electrostatic intermolecular interaction and this implication is discussed in terms of the multi-functionality of Fd in various redox metabolisms. PMID:26920048

  10. Electronic Structure and Energy Transfer in Europium(III)-Ciprofloxacin Complexes: A Theoretical Study.

    PubMed

    Emelina, Tatiana B; Freidzon, Alexandra Ya; Bagaturyants, Alexander A; Karasev, Vladimir E

    2016-09-29

    The structure and ligand-localized excited states of [Eu(cfqH) (cfq)(H2O)4]Cl2 (cfqH is ciprofloxacin) are studied by XMCQDPT2/CASSCF with full geometry optimization. The complex includes one anionic and one zwitterionic ligand. Two low-lying triplet states, both localized on the anionic ligand, are found. One of them has sufficient energy to transfer to the (5)D1 sublevel of Eu(3+), because its T-S0 vertical transition energy is equal (or very close) to the (7)F0-(5)D1 Eu(3+) excitation energy. The other triplet state has a very small S0-T1 gap, which favors fast nonradiative relaxation. Two other triplet states are localized on the zwitterionic ligand. One low-lying excited singlet state (S1) is localized on the anionic ligand; the other excited singlet is localized on the zwitterionic one. Spin-orbit coupling constants were calculated for the relaxed geometry of each state (ground state, two low-lying triplets, and one low-lying excited singlet) by spin-orbit configuration interaction (CI) with Pauli-Breit Hamiltonian. Large spin-orbit coupling constants between S1 and both triplets together with small energy gaps are indicative of fast intersystem crossing (ISC) from the excited singlet state to the triplet manifold. This ISC process is followed by energy transfer from the ligand-localized triplet states to the (5)D1 sublevel of Eu(3+). However, relatively large spin-orbit coupling constants between S0 and one of the triplet states together with the small T-S0 energy gap shows that this state can decay without transferring its energy to Eu(3+). This mechanism is expected to be common for other Ln(3+)-fluoroquinolone complexes.

  11. Asymmetric transfer hydrogenation of ketones catalyzed by enantiopure osmium(II) pybox complexes.

    PubMed

    Vega, Esmeralda; Lastra, E; Gamasa, M Pilar

    2013-05-20

    The complexes trans-[OsCl2(L){(S,S)-(i)Pr-pybox}] ((S,S)-(i)Pr-pybox = 2,6-bis[4'-(S)-isopropyloxazolin-2'-yl]pyridine, L = P(OMe)3 (1a), P(OEt)3 (2a), P(O(i)Pr)3 (3a), P(OPh)3 (4a), and cis-[OsCl2(L){(S,S)-(i)Pr-pybox}] (L = PPh3 (5a), P(i)Pr3 (6a), and PCy3 (7a)) have been synthesized from the complex trans-[OsCl2(η(2)-C2H4){(S,S)-(i)Pr-pybox}] via substitution of ethylene by phosphites and phosphines, respectively, under toluene reflux conditions. On the other hand, the synthesis of the complexes trans-[OsCl2(L){(R,R)-Ph-pybox}] (L = P(OMe)3 (1b) and cis-[OsCl2(L){(R,R)-Ph-pybox}] (L = PPh3 (5b), P(i)Pr3 (6b), and PCy3 (7b)) has been achieved from the complex trans-[OsCl2(η(2)-C2H4){(R,R)-Ph-pybox}] ((R,R)-Ph-pybox = 2,6-bis[4'-(R)-phenyloxazolin-2'-yl]pyridine under microwave irradiation. Complexes 1a-6a, 1b, 5b, and 6b have been assayed as catalysts for the asymmetric transfer hydrogenation (ATH) of ketones. Among the catalysts tested, the (i)Pr-pybox complexes trans-[OsCl2(L){(S,S)-(i)Pr-pybox}] (L = P(OMe)3 (1a), P(OEt)3 (2a), P(O(i)Pr)3 (3a), P(OPh)3 (4a)) have proven to be the most active catalysts for the reduction of a variety of aromatic ketones as nearly complete conversion and high enantioselectivity (up to 94%) are reached.

  12. 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.

  13. 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.

  14. Exosomes and microvesicles: extracellular vesicles for genetic information transfer and gene therapy.

    PubMed

    Lee, Yi; El Andaloussi, Samir; Wood, Matthew J A

    2012-10-15

    Exosomes and microvesicles are extracellular nanovesicles released by most but not all cells. They are specifically equipped to mediate intercellular communication via the transfer of genetic information, including the transfer of both coding and non-coding RNAs, to recipient cells. As a result, both exosomes and microvesicles play a fundamental biological role in the regulation of normal physiological as well as aberrant pathological processes, via altered gene regulatory networks and/or via epigenetic programming. For example, microvesicle-mediated genetic transfer can regulate the maintenance of stem cell plasticity and induce beneficial cell phenotype modulation. Alternatively, such vesicles play a role in tumor pathogenesis and the spread of neurodegenerative diseases via the transfer of specific microRNAs and pathogenic proteins. Given this natural property for genetic information transfer, the possibility of exploiting these vesicles for therapeutic purposes is now being investigated. Stem cell-derived microvesicles appear to be naturally equipped to mediate tissue regeneration under certain conditions, while recent evidence suggests that exosomes might be harnessed for the targeted delivery of human genetic therapies via the introduction of exogenous genetic cargoes such as siRNA. Thus, extracellular vesicles are emerging as potent genetic information transfer agents underpinning a range of biological processes and with therapeutic potential.

  15. 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

  16. Dissecting the kinetics of the NADP(+)-FADH2 charge transfer complex and flavin semiquinones in neuronal nitric oxide synthase.

    PubMed

    Li, Huiying; Jamal, Joumana; Chreifi, Georges; Venkatesh, Vikram; Abou-Ziab, Hoda; Poulos, Thomas L

    2013-07-01

    Electron flow within the neuronal nitric oxide synthase reductase domain (nNOSrd) includes hydride transfer from NADPH to FAD followed by two one-electron transfer reactions from FAD to FMN. We have used stopped flow spectrometry to closely monitor these electron transfer steps for both the wild type and the ΔG810 mutant of nNOSrd using a protocol involving both global analyses of the photodiode array spectral scans and curve fittings of single wavelength kinetic traces. The charge transfer complex and interflavin electron transfer events recorded at 750nm and 600nm, respectively, show the kinetics in different time frames. All electron transfer events are slow enough at 4°C to enable measurements of rate constants even for the fast charge transfer event. To our knowledge this is the first time the rate constants for the charge transfer between NADP(+) and FADH2 have been determined for NOS. These procedures allow us to conclude that (1) binding of the second NADPH is necessary to drive the full reduction of FMN and; (2) charge transfer and the subsequent interflavin electron transfer have distinct spectral features that can be monitored separately with stopped flow spectroscopy. These studies also enable us to conclude that interflavin electron transfer reported at 600nm is not limiting in NOS catalysis.

  17. 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).

  18. Methods of Information Geometry to model complex shapes

    NASA Astrophysics Data System (ADS)

    De Sanctis, A.; Gattone, S. A.

    2016-09-01

    In this paper, a new statistical method to model patterns emerging in complex systems is proposed. A framework for shape analysis of 2- dimensional landmark data is introduced, in which each landmark is represented by a bivariate Gaussian distribution. From Information Geometry we know that Fisher-Rao metric endows the statistical manifold of parameters of a family of probability distributions with a Riemannian metric. Thus this approach allows to reconstruct the intermediate steps in the evolution between observed shapes by computing the geodesic, with respect to the Fisher-Rao metric, between the corresponding distributions. Furthermore, the geodesic path can be used for shape predictions. As application, we study the evolution of the rat skull shape. A future application in Ophthalmology is introduced.

  19. 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.

  20. 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.

  1. 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

  2. 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

  3. Comparative analyses suggest that information transfer promoted sociality in male bats in the temperate zone.

    PubMed

    Safi, Kamran; Kerth, Gerald

    2007-09-01

    The evolution of sociality is a central theme in evolutionary biology. The vast majority of bats are social, which has been explained in terms of the benefits of communal breeding. However, the causes for segregated male groups remain unknown. In a comparative study, we tested whether diet and morphological adaptations to specific foraging styles, two factors known to influence the occurrence of information transfer, can predict male sociality. Our results suggest that the species most likely to benefit from information transfer--namely, those preying on ephemeral insects and with morphological adaptations to feeding in open habitat--are more likely to form male groups. Our findings also indicate that solitary life was the ancestral state of males and sociality evolved in several lineages. Beyond their significance for explaining the existence of male groups in bats, our findings highlight the importance of information transfer in the evolution of animal sociality.

  4. Aging, genetics, and the environment: potential of errors introduced into genetic information transfer by metal ions.

    PubMed

    Eichhorn, G L

    1979-02-01

    Metal ions, which are introduced into living organisms from the environment, are required in every aspect of genetic information transfer. However, the "wrong" metal ion, or even the "right" metal ion in the wrong concentration, can produce deleterious information transfer effects. Metal ions react with nucleic acids in many different ways, and virtually all of these reactions effect major changes in the structure of the nucleic acids. Cellular metal ion concentrations change with age. The effects of such concentration changes on genetic information transfer suggest the possibility that metal ions can influence the aging process. A specific example of such influence is the accumulation in brain cells of aluminum ions, which may have a relationship to Alzheimer's disease.

  5. 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.

  6. Utilization of charge-transfer complexation in the spectrophotometric determination of some monosaccharides through their osazone intermediates.

    PubMed

    Ayad, M; Belal, S; El Kheir, A A; El Adl, S

    1987-09-01

    Monosaccharide osazones are utilized in the spectrophotometric determination of their parent compounds though charge-transfer complexation with two-electron acceptor reagents. The molar combining ratio and the optimum complexation conditions have been studied. The method has been used to analyse for glucose and fructose and in determining blood glucose. PMID:18964408

  7. 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.

  8. 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

  9. 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.

  10. Simulation of the cavity-binding site of three bacterial multicopper oxidases upon complex stabilization: interactional profile and electron transference pathways.

    PubMed

    Bello, Martiniano; Correa-Basurto, Jose; Rudiño-Piñera, Enrique

    2014-01-01

    Previous studies have shown that multicopper oxidases (MCOs) oxidize organic and inorganic compounds through oxidation-reduction reactions in which three structurally and functionally arranged copper centers coordinate the uptake of an electron from a reduced substrate. Structural comparisons among three bacterial MCOs, with high structural homology and available three-dimensional information, reveal that the primary structural differences between these MCOs are located near the mononuclear copper center (T1Cu), where substrate oxidation occurs, as opposed to where the reduction of oxygen to water occurs at the trinuclear center. Nevertheless, this substrate oxidation is achieved through an outer-sphere electron transfer mechanism that does not generate a stable substrate-enzyme complex. In this study, MCOs from Thermus thermophilus (Tth-MCO), Bacillus subtilis (CotA), and Escherichia coli (CueO), which have been previously determined through X-ray crystallography, were used as models to analyze the binding modes of these MCOs to three organic molecules, with specific interest in the substrate-binding site. The binding mode of the electron-donor molecule to the electron transfer binding site was primarily attributed to hydrophobic contacts, which likely play an important role in the determination of substrate specificity. Some complexes generated in this study showed an electron donor molecule conformation in which an electron could be directly transferred to the histidines coordinating T1Cu, while for others additional electron transference pathways were also possible through the participation of charged residues during electron transfer.

  11. 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.

  12. Quantum effects in energy and charge transfer in an artificial photosynthetic complex

    NASA Astrophysics Data System (ADS)

    Ghosh, Pulak Kumar; Smirnov, Anatoly Yu.; Nori, Franco

    2011-06-01

    We investigate the quantum dynamics of energy and charge transfer in a wheel-shaped artificial photosynthetic antenna-reaction center complex. This complex consists of six light-harvesting chromophores and an electron-acceptor fullerene. To describe quantum effects on a femtosecond time scale, we derive the set of exact non-Markovian equations for the Heisenberg operators of this photosynthetic complex in contact with a Gaussian heat bath. With these equations we can analyze the regime of strong system-bath interactions, where reorganization energies are of the order of the intersite exciton couplings. We show that the energy of the initially excited antenna chromophores is efficiently funneled to the porphyrin-fullerene reaction center, where a charge-separated state is set up in a few picoseconds, with a quantum yield of the order of 95%. In the single-exciton regime, with one antenna chromophore being initially excited, we observe quantum beatings of energy between two resonant antenna chromophores with a decoherence time of ˜100 fs. We also analyze the double-exciton regime, when two porphyrin molecules involved in the reaction center are initially excited. In this regime we obtain pronounced quantum oscillations of the charge on the fullerene molecule with a decoherence time of about 20 fs (at liquid nitrogen temperatures). These results show a way to directly detect quantum effects in artificial photosynthetic systems.

  13. [Ultraviolet spectral characteristics of charge-transfer reaction complex in micellar system and its application].

    PubMed

    Du, Li-ming; Chen, Cai-ping; Li, Jian-hua

    2005-02-01

    Charge-transfer (CT) reaction of chloranil (TCBQ) as a pi-electron acceptor with fleroxacin (FLX) as an electron donor has been studied by ultraviolet spectrophotometry method. Experiment showed that FLX reacted with TCBQ in sodium dodecyl sulfate (SDS) micellar systems, and a stable complex was formed and the absorbency was remarkably enhanced. Therefore, a simple, rapid, accurate and sensitive method for the determination of FLX has been developed. Beer's law is obeyed in the range of 0.6-24 mg x L(-1) of FLX and r = 0.9993. The apparent molar absorptivity of CT complexes at 326 nm is 3.3 x 10(4) L x mol(-1) x cm(-1). The composition of CT complex was found to be 1:1 by Bent-French and curved intersection methods. The proposed method has been applied to the determination of ESL in tablets. The recoveries are 99.2%-99.7%. The relative standard deviation is 0.7%-2.1%. The proposed methods are suitable for the routine quality control of drug alone and in tablets or capsules without fear of interference caused by the excipients expected to be present in tablets or capsules.

  14. 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.

  15. Charge transfer complexes of fullerene[60] with porphyrins as molecular rectifiers. A theoretical study.

    PubMed

    Montiel, Filiberto; Fomina, Lioudmila; Fomine, Serguei

    2015-01-01

    Molecular diodes based on charge transfer complexes of fullerene[60] with different metalloporphyrins have been modeled. Their current-voltage characteristics and the rectification ratios (RR) were calculated using direct ab initio method at PBE/def2-SVP level of theory with D3 dispersion correction, for voltages ranging from -2 to +2 V. The highest RR of 32.5 was determined for the complex of fullerene[60] with zinc tetraphenylporphyrin at 0.8 V. Other molecular diodes possessed lower RR, however, all complexes showed RR higher than 1 at all bias voltages. The asymmetric evolutions and alignment of the molecular orbitals with the applied bias were found to be essential for generating the molecular diode rectification behavior. Metal nature of metalloporphyrins and the interaction porphyrin-electrode significantly affect RR of molecular diode. Large metal ions like Cd(2+) and Ag(2+) in metalloporphyrins disfavor rectification creating conducting channels in two directions, while smaller ions Zn(2+) and Cu(2+) favor rectification increasing the interaction between gold electrode and porphyrin macrocycle.

  16. 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)].

  17. Generation of a high-valent iron imido corrolazine complex and NR group transfer reactivity.

    PubMed

    Leeladee, Pannee; Jameson, Guy N L; Siegler, Maxime A; Kumar, Devesh; de Visser, Sam P; Goldberg, David P

    2013-04-15

    The generation of a new high-valent iron terminal imido complex prepared with a corrolazine macrocycle is reported. The reaction of [Fe(III)(TBP8Cz)] (TBP8Cz = octakis(4-tert-butylphenyl)corrolazinato) with the commercially available chloramine-T (Na(+)TsNCl(-)) leads to oxidative N-tosyl transfer to afford [Fe(IV)(TBP8Cz(+•))(NTs)] in dichloromethane/acetonitrile at room temperature. This complex was characterized by UV-vis, Mössbauer (δ = -0.05 mm s(-1), ΔE(Q) = 2.94 mm s(-1)), and EPR (X-band (15 K), g = 2.10, 2.00) spectroscopies, and together with reactivity patterns and DFT calculations has been established as an iron(IV) species antiferromagnetically coupled with a Cz-π-cation-radical (S(total) = 1/2 ground state). Reactivity studies with triphenylphosphine as substrate show that [Fe(IV)(TBP8Cz(+•))(NTs)] is an efficient NTs transfer agent, affording the phospharane product Ph3P═NTs under both stoichiometric and catalytic conditions. Kinetic analysis of this reaction supports a bimolecular NTs transfer mechanism with rate constant of 70(15) M(-1) s(-1). These data indicate that [Fe(IV)(TBP8Cz(+•))(NTs)] reacts about 100 times faster than analogous Mn terminal arylimido corrole analogues. It was found that two products crystallize from the same reaction mixture of Fe(III)(TBP8Cz) + chloramine-T + PPh3, [Fe(IV)(TBP8Cz)(NPPh3)] and [Fe(III)(TBP8Cz)(OPPh3)], which were definitively characterized by X-ray crystallography. The sequential production of Ph3P═NTs, Ph3P═NH, and Ph3P═O was observed by (31)P NMR spectroscopy and led to a proposed mechanism that accounts for all of the observed products. The latter Fe(III) complex was then rationally synthesized and structurally characterized from Fe(III)(TBP8Cz) and OPPh3, providing an important benchmark compound for spectroscopic studies. A combination of Mössbauer and EPR spectroscopies led to the characterization of both intermediate spin (S = 3/2 and low spin (S = 1/2) Fe(III) corrolazines, as

  18. Generation of a high-valent iron imido corrolazine complex and NR group transfer reactivity.

    PubMed

    Leeladee, Pannee; Jameson, Guy N L; Siegler, Maxime A; Kumar, Devesh; de Visser, Sam P; Goldberg, David P

    2013-04-15

    The generation of a new high-valent iron terminal imido complex prepared with a corrolazine macrocycle is reported. The reaction of [Fe(III)(TBP8Cz)] (TBP8Cz = octakis(4-tert-butylphenyl)corrolazinato) with the commercially available chloramine-T (Na(+)TsNCl(-)) leads to oxidative N-tosyl transfer to afford [Fe(IV)(TBP8Cz(+•))(NTs)] in dichloromethane/acetonitrile at room temperature. This complex was characterized by UV-vis, Mössbauer (δ = -0.05 mm s(-1), ΔE(Q) = 2.94 mm s(-1)), and EPR (X-band (15 K), g = 2.10, 2.00) spectroscopies, and together with reactivity patterns and DFT calculations has been established as an iron(IV) species antiferromagnetically coupled with a Cz-π-cation-radical (S(total) = 1/2 ground state). Reactivity studies with triphenylphosphine as substrate show that [Fe(IV)(TBP8Cz(+•))(NTs)] is an efficient NTs transfer agent, affording the phospharane product Ph3P═NTs under both stoichiometric and catalytic conditions. Kinetic analysis of this reaction supports a bimolecular NTs transfer mechanism with rate constant of 70(15) M(-1) s(-1). These data indicate that [Fe(IV)(TBP8Cz(+•))(NTs)] reacts about 100 times faster than analogous Mn terminal arylimido corrole analogues. It was found that two products crystallize from the same reaction mixture of Fe(III)(TBP8Cz) + chloramine-T + PPh3, [Fe(IV)(TBP8Cz)(NPPh3)] and [Fe(III)(TBP8Cz)(OPPh3)], which were definitively characterized by X-ray crystallography. The sequential production of Ph3P═NTs, Ph3P═NH, and Ph3P═O was observed by (31)P NMR spectroscopy and led to a proposed mechanism that accounts for all of the observed products. The latter Fe(III) complex was then rationally synthesized and structurally characterized from Fe(III)(TBP8Cz) and OPPh3, providing an important benchmark compound for spectroscopic studies. A combination of Mössbauer and EPR spectroscopies led to the characterization of both intermediate spin (S = 3/2 and low spin (S = 1/2) Fe(III) corrolazines, as

  19. Electron transfer from the water oxidizing complex at cryogenic temperatures: the S1 to S2 step.

    PubMed

    Nugent, Jonathan H A; Muhiuddin, Irine P; Evans, Michael C W

    2002-03-26

    We report the detection of a "split" electron paramagnetic resonance (EPR) signal during illumination of dark-adapted (S(1) state) oxygen-evolving photosystem II (PSII) membranes at <20 K. The characteristics of this signal indicate that it arises from an interaction between an organic radical and the Mn cluster of PSII. The broad radical signal decays in the dark following illumination either by back-reaction with Qa*- or by forward electron transfer from the Mn cluster. The forward electron transfer (either from illumination at 11 K followed by incubation in the dark at 77 K or by illumination at 77 K) results in the formation of a multiline signal similar to, but distinct from, other well-characterized multiline forms found in the S0 and S2 states. The relative yield of the "S1 split signal", which we provisionally assign to S1X*, where X could be YZ* or Car*+, and that of the 77 K multiline signal indicate a relationship between the two states. An approximate quantitation of the yield of these signals indicates that up to 40-50% of PSII centers can form the S1 split signal. Ethanol addition removes the ability to observe the S1 split signal, but the multiline signal is still formed at 77 K. The multiline forms with <700 nm light and is not affected by near-infrared (IR) light, showing that we are detecting electron transfer in centers not responsive to IR illumination. The results provide important new information about the mechanism of electron abstraction from the water oxidizing complex (WOC).

  20. 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

  1. Information transfer via implicit encoding with delay time modulation in a time-delay system

    NASA Astrophysics Data System (ADS)

    Kye, Won-Ho

    2012-08-01

    A new encoding scheme for information transfer with modulated delay time in a time-delay system is proposed. In the scheme, the message is implicitly encoded into the modulated delay time. The information transfer rate as a function of encoding redundancy in various noise scales is presented and it is analyzed that the implicit encoding scheme (IES) has stronger resistance against channel noise than the explicit encoding scheme (EES). In addition, its advantages in terms of secure communication and feasible applications are discussed.

  2. 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.

  3. Long-distance quantum information transfer with strong coupling hybrid solid system.

    PubMed

    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

  4. 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.

  5. 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

  6. Power laws of complex systems from extreme physical information

    NASA Astrophysics Data System (ADS)

    Frieden, B. Roy; Gatenby, Robert A.

    2005-09-01

    Many complex systems obey allometric, or power, laws y=Yxa . Here y⩾0 is the measured value of some system attribute a , Y⩾0 is a constant, and x is a stochastic variable. Remarkably, for many living systems the exponent a is limited to values n/4 , n=0,±1,±2,… . Here x is the mass of a randomly selected creature in the population. These quarter-power laws hold for many attributes, such as pulse rate (n=-1) . Allometry has, in the past, been theoretically justified on a case-by-case basis. An ultimate goal is to find a common cause for allometry of all types and for both living and nonliving systems. The principle I-J=extremum of extreme physical information is found to provide such a cause. It describes the flow of Fisher information J→I from an attribute value a on the cell level to its exterior observation y . Data y are formed via a system channel function y≡f(x,a) , with f(x,a) to be found. Extremizing the difference I-J through variation of f(x,a) results in a general allometric law f(x,a)≡y=Yxa . Darwinian evolution is presumed to cause a second extremization of I-J , now with respect to the choice of a . The solution is a=n/4 , n=0,±1,±2… , defining the particular powers of biological allometry. Under special circumstances, the model predicts that such biological systems are controlled by only two distinct intracellular information sources. These sources are conjectured to be cellular DNA and cellular transmembrane ion gradients

  7. Power laws of complex systems from extreme physical information.

    PubMed

    Frieden, B Roy; Gatenby, Robert A

    2005-09-01

    Many complex systems obey allometric, or power, laws y=Y x(a) . Here y > or = 0 is the measured value of some system attribute a , Y> or =0 is a constant, and x is a stochastic variable. Remarkably, for many living systems the exponent a is limited to values n/4 , n=0, +/-1, +/-2.... Here x is the mass of a randomly selected creature in the population. These quarter-power laws hold for many attributes, such as pulse rate (n=-1) . Allometry has, in the past, been theoretically justified on a case-by-case basis. An ultimate goal is to find a common cause for allometry of all types and for both living and nonliving systems. The principle I-J=extremum of extreme physical information is found to provide such a cause. It describes the flow of Fisher information J-->I from an attribute value a on the cell level to its exterior observation y . Data y are formed via a system channel function y identical to f (x,a) , with f (x,a) to be found. Extremizing the difference I-J through variation of f (x,a) results in a general allometric law f (x,a) identical to y=Y x(a) . Darwinian evolution is presumed to cause a second extremization of I-J , now with respect to the choice of a . The solution is a=n/4 , n=0,+/-1,+/-2..., defining the particular powers of biological allometry. Under special circumstances, the model predicts that such biological systems are controlled by only two distinct intracellular information sources. These sources are conjectured to be cellular DNA and cellular transmembrane ion gradients. PMID:16241509

  8. Photoinduced electron transfer from N,N-dimethylaniline to 7-amino Coumarins in protein-surfactant complex: Slowing down of electron transfer dynamics compared to micelles

    NASA Astrophysics Data System (ADS)

    Chakraborty, Anjan; Seth, Debabrata; Setua, Palash; Sarkar, Nilmoni

    2006-02-01

    Photoinduced electron transfer from N,N-dimethylaniline to different Coumarin dyes has been investigated in dodecyl trimethyl ammonium bromide (DTAB) micelles and in Bovine serum albumin (BSA)-DTAB protein-surfactant complex using steady-state and picosecond time-resolved fluorescence spectroscopy. We observed a slower fluorescence quenching rate in the DTAB micelles and in the protein-surfactant complex as compared to that in pure acetonitrile solution. Moreover, the observed fluorescence quenching in BSA-DTAB complex was found to be slower than that in DTAB micelles. In the correlation of free-energy change with the fluorescence quenching constant we observed a deviation in the fluorescence quenching electron transfer rate for Coumarin 151 (C-151) from the normal Marcus curve. This observation is ascribed to the stronger interaction of C-151 with the surfactant molecules present in the micelles. This is evident from the slower translation diffusion (DL) of Coumarin 151 compared to other probe molecules.

  9. Empirical and Theoretical Aspects of Generation and Transfer of Information in a Neuromagnetic Source Network

    PubMed Central

    Vakorin, Vasily A.; Mišić, Bratislav; Krakovska, Olga; McIntosh, Anthony Randal

    2011-01-01

    Variability in source dynamics across the sources in an activated network may be indicative of how the information is processed within a network. Information-theoretic tools allow one not only to characterize local brain dynamics but also to describe interactions between distributed brain activity. This study follows such a framework and explores the relations between signal variability and asymmetry in mutual interdependencies in a data-driven pipeline of non-linear analysis of neuromagnetic sources reconstructed from human magnetoencephalographic (MEG) data collected as a reaction to a face recognition task. Asymmetry in non-linear interdependencies in the network was analyzed using transfer entropy, which quantifies predictive information transfer between the sources. Variability of the source activity was estimated using multi-scale entropy, quantifying the rate of which information is generated. The empirical results are supported by an analysis of synthetic data based on the dynamics of coupled systems with time delay in coupling. We found that the amount of information transferred from one source to another was correlated with the difference in variability between the dynamics of these two sources, with the directionality of net information transfer depending on the time scale at which the sample entropy was computed. The results based on synthetic data suggest that both time delay and strength of coupling can contribute to the relations between variability of brain signals and information transfer between them. Our findings support the previous attempts to characterize functional organization of the activated brain, based on a combination of non-linear dynamics and temporal features of brain connectivity, such as time delay. PMID:22131968

  10. 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.

  11. 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.

  12. Information transfer about roosts in female Bechstein's bats: an experimental field study.

    PubMed Central

    Kerth, Gerald; Reckardt, Karsten

    2003-01-01

    Information transfer among group members is believed to play an important part in the evolution of coloniality in both birds and bats. Although information transfer has received much scientific interest, field studies using experiments to test the underlying hypotheses are rare. We used a field experiment to test if communally breeding female Bechstein's bats (Myotis bechsteinii) exchange information regarding novel roosts. We supplied a wild colony, comprising 17 adult females of known relatedness, with pairs of suitable and unsuitable roosts and monitored the arrival of individuals marked with transponders (PIT-tags) over 2 years. As expected with information transfer, significantly more naive females were recruited towards suitable than towards unsuitable roosts. We conclude that information transfer about roosts has two functions: (i) it generates communal knowledge of a large set of roosts; and (ii) it aids avoidance of colony fission during roost switching. Both functions seem important in Bechstein's bats, in which colonies depend on many day roosts and where colony members live together for many years. PMID:12641906

  13. 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.

  14. 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.

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  19. 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

  20. 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).

  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. Coordination Sphere Tuning of the Electron Transfer Dissociation Behavior of Cu(II)-Peptide Complexes

    PubMed Central

    Dong, Jia; Vachet, Richard W.

    2011-01-01

    In contrast to previous electron capture dissociation (ECD) studies, we find that electron transfer dissociation (ETD) of Cu(II)-peptide complexes can generate c- and z- type product ions when the peptide has a sufficient number of strongly coordinating residues. Double-resonance experiments, ion-molecule reactions, and collision-induced dissociation (CID) prove that the c and z product ions are formed via typical radical pathways without the associated reduction of Cu(II), despite the high second ionization energy of Cu. A positive correlation between the number of Cu(II) binding groups in the peptide sequence and the extent of c and z ion formation was also observed. This trend is rationalized by considering that the recombination energy of Cu(II) can be lowered by strong binding ligands to an extent that enables electron transfer to non-Cu sites (e.g. protonation sites) to compete with Cu(II) reduction, thereby generating c/z ions in a manner similar to that observed for protonated (i.e. non-metalated) peptides. PMID:22161629

  3. Coordination Sphere Tuning of the Electron Transfer Dissociation Behavior of Cu(II)-Peptide Complexes

    NASA Astrophysics Data System (ADS)

    Dong, Jia; Vachet, Richard W.

    2012-02-01

    In contrast to previous electron capture dissociation (ECD) studies, we find that electron transfer dissociation (ETD) of Cu(II)-peptide complexes can generate c- and z-type product ions when the peptide has a sufficient number of strongly coordinating residues. Double-resonance experiments, ion-molecule reactions, and collision-induced dissociation (CID) prove that the c and z product ions are formed via typical radical pathways without the associated reduction of Cu(II), despite the high second ionization energy of Cu. A positive correlation between the number of Cu(II) binding groups in the peptide sequence and the extent of c and z ion formation was also observed. This trend is rationalized by considering that the recombination energy of Cu(II) can be lowered by strong binding ligands to an extent that enables electron transfer to non-Cu sites (e.g., protonation sites) to compete with Cu(II) reduction, thereby generating c/z ions in a manner similar to that observed for protonated (i.e., nonmetalated) peptides.

  4. 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

  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. 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

  7. Low light adaptation: energy transfer processes in different types of light harvesting complexes from Rhodopseudomonas palustris.

    PubMed

    Moulisová, Vladimíra; Luer, Larry; Hoseinkhani, Sajjad; Brotosudarmo, Tatas H P; Collins, Aaron M; Lanzani, Guglielmo; Blankenship, Robert E; Cogdell, Richard J

    2009-12-01

    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.

  8. 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

  9. 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.

  10. Probing energy transfer events in the light harvesting complex 2 (LH2) of Rhodobacter sphaeroides with two-dimensional spectroscopy.

    PubMed

    Fidler, Andrew F; Singh, Ved P; Long, Phillip D; Dahlberg, Peter D; Engel, Gregory S

    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.

  11. Effective field theory models for nonviolent information transfer from black holes

    NASA Astrophysics Data System (ADS)

    Giddings, Steven B.; Shi, Yinbo

    2014-06-01

    Transfer of quantum information from the interior of a black hole to its atmosphere is described, in models based on effective field theory. This description illustrates that such transfer need not be violent to the semiclassical geometry or to infalling observers, and in particular can avoid producing a singular horizon or "firewall". One can specifically quantify the rate of information transfer and show that a rate necessary to unitarize black hole evaporation produces a relatively mild modification to the stress tensor near the horizon. In an exterior description of the transfer, the new interactions responsible for it are approximated by "effective sources" acting on fields in the black hole atmosphere. If the necessary interactions couple to general modes in the black hole atmosphere, one also finds a straightforward mechanism for information transfer rates to increase when a black hole is mined, avoiding paradoxical behavior. Correspondence limits are discussed, in the presence of such new interactions, for both small black holes and large ones; the near-horizon description of the latter is approximately that of Rindler space.

  12. Complex Förster energy transfer interactions between semiconductor quantum dots and a redox-active osmium assembly.

    PubMed

    Stewart, Michael H; Huston, Alan L; Scott, Amy M; Efros, Alexander L; Melinger, Joseph S; Gemmill, Kelly Boeneman; Trammell, Scott A; Blanco-Canosa, Juan B; Dawson, Philip E; Medintz, Igor L

    2012-06-26

    The ability of luminescent semiconductor quantum dots (QDs) to engage in diverse energy transfer processes with organic dyes, light-harvesting proteins, metal complexes, and redox-active labels continues to stimulate interest in developing them for biosensing and light-harvesting applications. Within biosensing configurations, changes in the rate of energy transfer between the QD and the proximal donor, or acceptor, based upon some external (biological) event form the principle basis for signal transduction. However, designing QD sensors to function optimally is predicated on a full understanding of all relevant energy transfer mechanisms. In this report, we examine energy transfer between a range of CdSe-ZnS core-shell QDs and a redox-active osmium(II) polypyridyl complex. To facilitate this, the Os complex was synthesized as a reactive isothiocyanate and used to label a hexahistidine-terminated peptide. The Os-labeled peptide was ratiometrically self-assembled to the QDs via metal affinity coordination, bringing the Os complex into close proximity of the nanocrystal surface. QDs displaying different emission maxima were assembled with increasing ratios of Os-peptide complex and subjected to detailed steady-state, ultrafast transient absorption, and luminescence lifetime decay analyses. Although the possibility exists for charge transfer quenching interactions, we find that the QD donors engage in relatively efficient Förster resonance energy transfer with the Os complex acceptor despite relatively low overall spectral overlap. These results are in contrast to other similar QD donor-redox-active acceptor systems with similar separation distances, but displaying far higher spectral overlap, where charge transfer processes were reported to be the dominant QD quenching mechanism.

  13. Pathways for energy transfer in the core light-harvesting complexes CP43 and CP47 of photosystem II.

    PubMed

    de Weerd, Frank L; van Stokkum, Ivo H M; van Amerongen, Herbert; Dekker, Jan P; van Grondelle, Rienk

    2002-03-01

    The pigment-protein complexes CP43 and CP47 transfer excitation energy from the peripheral antenna of photosystem II toward the photochemical reaction center. We measured the excitation dynamics of the chlorophylls in isolated CP43 and CP47 complexes at 77 K by time-resolved absorbance-difference and fluorescence spectroscopy. The spectral relaxation appeared to occur with rates of 0.2-0.4 ps and 2-3 ps in both complexes, whereas an additional relaxation of 17 ps was observed only in CP47. Using the 3.8-A crystal structure of the photosystem II core complex from Synechococcus elongatus (A. Zouni, H.-T. Witt, J. Kern, P. Fromme, N. Krauss, W. Saenger, and P. Orth, 2001, Nature, 409:739-743), excitation energy transfer kinetics were calculated and a Monte Carlo simulation of the absorption spectra was performed. In both complexes, the rate of 0.2-0.4 ps can be ascribed to excitation energy transfer within a layer of chlorophylls near the stromal side of the membrane, and the slower 2-3-ps process to excitation energy transfer to the calculated lowest excitonic state. We conclude that excitation energy transfer within CP43 and CP47 is fast and does not contribute significantly to the well-known slow trapping of excitation energy in photosystem II.

  14. Report of a Planning Conference for Solar Technology Information Transfer. Austin, Texas, 12-13 June 1979).

    ERIC Educational Resources Information Center

    Southwestern Library Association, Stillwater, OK.

    Charged with the responsibility of determining the best way to plan for solar technology information transfer within the state of Texas, participants in the Planning Conference for Solar Technology Information Transfer met to discuss the many ongoing activities related to energy information dissemination, to analyze the resources available in…

  15. Geometry and quadratic nonlinearity of charge transfer complexes in solution using depolarized hyper-Rayleigh scattering.

    PubMed

    Pandey, Ravindra; Ghosh, Sampa; Mukhopadhyay, S; Ramasesha, S; Das, Puspendu K

    2011-01-28

    We report large quadratic nonlinearity in a series of 1:1 molecular complexes between methyl substituted benzene donors and quinone acceptors in solution. The first hyperpolarizability, β(HRS), which is very small for the individual components, becomes large by intermolecular charge transfer (CT) interaction between the donor and the acceptor in the complex. In addition, we have investigated the geometry of these CT complexes in solution using polarization resolved hyper-Rayleigh scattering (HRS). Using linearly (electric field vector along X direction) and circularly polarized incident light, respectively, we have measured two macroscopic depolarization ratios D=I(2ω,X,X)/I(2ω,Z,X) and D(')=I(2ω,X,C)/I(2ω,Z,C) in the laboratory fixed XYZ frame by detecting the second harmonic scattered light in a polarization resolved fashion. The experimentally obtained first hyperpolarizability, β(HRS), and the value of macroscopic depolarization ratios, D and D('), are then matched with the theoretically deduced values from single and double configuration interaction calculations performed using the Zerner's intermediate neglect of differential overlap self-consistent reaction field technique. In solution, since several geometries are possible, we have carried out calculations by rotating the acceptor moiety around three different axes keeping the donor molecule fixed at an optimized geometry. These rotations give us the theoretical β(HRS), D and D(') values as a function of the geometry of the complex. The calculated β(HRS), D, and D(') values that closely match with the experimental values, give the dominant equilibrium geometry in solution. All the CT complexes between methyl benzenes and chloranil or 1,2-dichloro-4,5-dicyano-p-benzoquinone investigated here are found to have a slipped parallel stacking of the donors and the acceptors. Furthermore, the geometries are staggered and in some pairs, a twist angle as high as 30° is observed. Thus, we have demonstrated in

  16. 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…

  17. Information transfer between neurons in the motor cortex triggered by visual cues.

    PubMed

    Kim, Sanggyun; Takahashi, Kazutaka; Hatsopoulos, Nicholas G; Coleman, Todd P

    2011-01-01

    It was previously shown that beta oscillations of local field potentials in the arm area of the primary motor cortex (MI) of nonhuman primates propagate as travelling waves across MI of monkeys during movement preparation and execution and are believed to subserve cortical information transfer. To investigate the information transfer and its change over time at the single-cell level, we analyzed simultaneously recorded multiple MI neural spike trains of a monkey using a Granger causality measure for point process models before and after visual cues instructing the onset of reaching movements. In this analysis, we found that more pairs of neurons showed information transfer between them after appearances of upcoming movement targets than before, and the directions of the information transfer across neurons in MI were coincident with the directions of the propagating waves. These results suggest that the neuron pairs identified in the current study are the candidates of neurons that travel with spatiotemporal dynamics of beta oscillations in the MI.

  18. The Role of University Faculty in the Transfer of Technological Information.

    ERIC Educational Resources Information Center

    Sincoff, Michael Z.; Dajani, Jarir S.

    Examined in this paper are some of the factors which presently interact with, and which will continue to interact with, the transfer of technological information, with particular emphasis on those factors which play on the role of the university faculty member. Among these factors are the composition and goals of the student population the faculty…

  19. 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...

  20. 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.

  1. Collaboration for Student Success: A System for Providing Transfer Student Performance Information to Feeder Institutions.

    ERIC Educational Resources Information Center

    Thompson, Susan

    Southwest Texas State (SWT) University has developed a system of communication with two-year community colleges that aims to provide information about new student performance and identify student needs. About 60% of the 7,000 new undergraduate students first enrolling in SWT each year are transfer students. In 1992, about 60% of new students at…

  2. 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…

  3. 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…

  4. 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.

  5. 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.

  6. 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.

  7. Agostic interaction and intramolecular proton transfer from the protonation of dihydrogen ortho metalated ruthenium complexes

    PubMed Central

    Toner, Andrew; Matthes, Jochen; Gründemann, Stephan; Limbach, Hans-Heinrich; Chaudret, Bruno; Clot, Eric; Sabo-Etienne, Sylviane

    2007-01-01

    Protonation of the ortho-metalated ruthenium complexes RuH(H2)(X)(PiPr3)2 [X = 2-phenylpyridine (ph-py) (1), benzoquinoline (bq) (2)] and RuH(CO)(ph-py)(PiPr3)2 (3) with [H(OEt2)2]+[BAr′4]− (BAr′4 = [(3,5-(CF3)2C6H3)4B]) under H2 atmosphere yields the corresponding cationic hydrido dihydrogen ruthenium complexes [RuH(H2)(H-X)(PiPr3)2][BAr′4] [X = phenylpyridine (ph-py) (1-H); benzoquinoline (bq) (2-H)] and the carbonyl complex [RuH(CO)(H-ph-py)(PiPr3)2][BAr′4] (3-H). The complexes accommodate an agostic CH interaction characterized by NMR and in the case of 1-H by x-ray diffraction. Fluxional processes involve the hydride and dihydrogen ligands in 1-H and 2-H and the rotation of the phenyl ring displaying the agostic interaction in 1-H and 3-H. NMR studies (lineshape analysis of the temperature-dependent NMR spectra) and density functional theory calculations are used to understand these processes. Under vacuum, one equivalent of dihydrogen can be removed from 1-H and 2-H leading to the formation of the corresponding cationic ortho-metalated complexes [Ru(H2)(THF)(X)(PiPr3)2]+ [X = ph-py (1-THF), bq (2-THF)]. The reaction is fully reversible. Density functional theory calculations and NMR data give information about the reversible mechanism of CH activation in these ortho-metalated ruthenium complexes. Our study highlights the subtle interplay between key ligands such as hydrides, σ-dihydrogen, and agostic bonds, in CH activation processes. PMID:17360384

  8. Agostic interaction and intramolecular proton transfer from the protonation of dihydrogen ortho metalated ruthenium complexes.

    PubMed

    Toner, Andrew; Matthes, Jochen; Gründemann, Stephan; Limbach, Hans-Heinrich; Chaudret, Bruno; Clot, Eric; Sabo-Etienne, Sylviane

    2007-04-24

    Protonation of the ortho-metalated ruthenium complexes RuH(H(2))(X)(P(i)Pr(3))(2) [X = 2-phenylpyridine (ph-py) (1), benzoquinoline (bq) (2)] and RuH(CO)(ph-py)(P(i)Pr(3))(2) (3) with [H(OEt(2))(2)](+)[BAr'(4)](-) (BAr'(4) = [(3,5-(CF(3))(2)C(6)H(3))(4)B]) under H(2) atmosphere yields the corresponding cationic hydrido dihydrogen ruthenium complexes [RuH(H(2))(H-X)(P(i)Pr(3))(2)][BAr'(4)] [X = phenylpyridine (ph-py) (1-H); benzoquinoline (bq) (2-H)] and the carbonyl complex [RuH(CO)(H-ph-py)(P(i)Pr(3))(2)][BAr'(4)] (3-H). The complexes accommodate an agostic C H interaction characterized by NMR and in the case of 1-H by x-ray diffraction. Fluxional processes involve the hydride and dihydrogen ligands in 1-H and 2-H and the rotation of the phenyl ring displaying the agostic interaction in 1-H and 3-H. NMR studies (lineshape analysis of the temperature-dependent NMR spectra) and density functional theory calculations are used to understand these processes. Under vacuum, one equivalent of dihydrogen can be removed from 1-H and 2-H leading to the formation of the corresponding cationic ortho-metalated complexes [Ru(H(2))(THF)(X)(P(i)Pr(3))(2)](+) [X = ph-py (1-THF), bq (2-THF)]. The reaction is fully reversible. Density functional theory calculations and NMR data give information about the reversible mechanism of C H activation in these ortho-metalated ruthenium complexes. Our study highlights the subtle interplay between key ligands such as hydrides, sigma-dihydrogen, and agostic bonds, in C H activation processes. PMID:17360384

  9. TRENTOOL: A Matlab open source toolbox to analyse information flow in time series data with transfer entropy

    PubMed Central

    2011-01-01

    Background Transfer entropy (TE) is a measure for the detection of directed interactions. Transfer entropy is an information theoretic implementation of Wiener's principle of observational causality. It offers an approach to the detection of neuronal interactions that is free of an explicit model of the interactions. Hence, it offers the power to analyze linear and nonlinear interactions alike. This allows for example the comprehensive analysis of directed interactions in neural networks at various levels of description. Here we present the open-source MATLAB toolbox TRENTOOL that allows the user to handle the considerable complexity of this measure and to validate the obtained results using non-parametrical statistical testing. We demonstrate the use of the toolbox and the performance of the algorithm on simulated data with nonlinear (quadratic) coupling and on local field potentials (LFP) recorded from the retina and the optic tectum of the turtle (Pseudemys scripta elegans) where a neuronal one-way connection is likely present. Results In simulated data TE detected information flow in the simulated direction reliably with false positives not exceeding the rates expected under the null hypothesis. In the LFP data we found directed interactions from the retina to the tectum, despite the complicated signal transformations between these stages. No false positive interactions in the reverse directions were detected. Conclusions TRENTOOL is an implementation of transfer entropy and mutual information analysis that aims to support the user in the application of this information theoretic measure. TRENTOOL is implemented as a MATLAB toolbox and available under an open source license (GPL v3). For the use with neural data TRENTOOL seamlessly integrates with the popular FieldTrip toolbox. PMID:22098775

  10. 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

  11. Eu(III) complexes as anion-responsive luminescent sensors and paramagnetic chemical exchange saturation transfer agents.

    PubMed

    Hammell, Jacob; Buttarazzi, Leandro; Huang, Ching-Hui; Morrow, Janet R

    2011-06-01

    The Eu(III) complex of (1S,4S,7S,10S)-1,4,7,10-tetrakis(2-hydroxypropyl)-1,4,7,10-tetraazacyclododecane (S-THP) is studied as a sensor for biologically relevant anions. Anion interactions produce changes in the luminescence emission spectrum of the Eu(III) complex, in the (1)H NMR spectrum, and correspondingly, in the PARACEST spectrum of the complex (PARACEST = paramagnetic chemical exchange saturation transfer). Direct excitation spectroscopy and luminescence lifetime studies of Eu(S-THP) give information about the speciation and nature of anion interactions including carbonate, acetate, lactate, citrate, phosphate, and methylphosphate at pH 7.2. Data is consistent with the formation of both innersphere and outersphere complexes of Eu(S-THP) with acetate, lactate, and carbonate. These anions have weak dissociation constants that range from 19 to 38 mM. Citrate binding to Eu(S-THP) is predominantly innersphere with a dissociation constant of 17 μM. Luminescence emission peak changes upon addition of anion to Eu(S-THP) show that there are two distinct binding events for phosphate and methylphosphate with dissociation constants of 0.3 mM and 3.0 mM for phosphate and 0.6 mM and 9.8 mM for methyl phosphate. Eu(THPC) contains an appended carbostyril derivative as an antenna to sensitize Eu(III) luminescence. Eu(THPC) binds phosphate and citrate with dissociation constants that are 10-fold less than that of the Eu(S-THP) parent, suggesting that functionalization through a pendent group disrupts the anion binding site. Eu(S-THP) functions as an anion responsive PARACEST agent through exchange of the alcohol protons with bulk water. The alcohol proton resonances of Eu(S-THP) shift downfield in the presence of acetate, lactate, citrate, and methylphosphate, giving rise to distinct PARACEST peaks. In contrast, phosphate binds to Eu(S-THP) to suppress the PARACEST alcohol OH peak and carbonate does not markedly change the alcohol peak at 5 mM Eu(S-THP), 15 mM carbonate at p

  12. Spectroscopy of Photovoltaic Materials: Charge-Transfer Complexes and Titanium Dioxide

    NASA Astrophysics Data System (ADS)

    Dillon, Robert John

    The successful function of photovoltaic (PV) and photocatalytic (PC) systems centers primarily on the creation and photophysics of charge separated electron-hole pairs. The pathway leading to separate carriers varies by material; organic materials typically require multiple events to charge separate, whereas inorganic semiconductors can directly produce free carriers. In this study, time-resolved spectroscopy is used to provide insight into two such systems: 1) organic charge-transfer (CT) complexes, where electrons and holes are tightly bound to each other, and 2) Au-TiO2 core-shell nanostructures, where free carriers are directly generated. 1) CT complexes are structurally well defined systems consisting of donor molecules, characterized by having low ionization potentials, and acceptor molecules, characterized by having high electron affinities. Charge-transfer is the excitation of an electron from the HOMO of a donor material directly into the LUMO of the acceptor material, leading to an electron and hole separated across the donor:acceptor interface. The energy of the CT transition is often less than that of the bandgaps of donor and acceptor materials individually, sparking much interest if PV systems can utilize the CT band to generate free carriers from low energy photons. In this work we examine the complexes formed between acceptors tetracyanobenzene (TCNB) and tetracyanoquinodimethane (TCNQ) with several aromatic donors. We find excitation of the charge-transfer band of these systems leads to strongly bound electron-hole pairs that exclusively undergo recombination to the ground state. In the case of the TCNB complexes, our initial studies were flummoxed by the samples' generally low threshold for photo and mechanical damage. As our results conflicted with previous literature, a significant portion of this study was spent quantifying the photodegradation process. 2) Unlike the previous system, free carriers are directly photogenerated in TiO2, and the

  13. The Deceptively Simple N170 Reflects Network Information Processing Mechanisms Involving Visual Feature Coding and Transfer Across Hemispheres

    PubMed Central

    Ince, Robin A. A.; Jaworska, Katarzyna; Gross, Joachim; Panzeri, Stefano; van Rijsbergen, Nicola J.; Rousselet, Guillaume A.; Schyns, Philippe G.

    2016-01-01

    A key to understanding visual cognition is to determine “where”, “when”, and “how” brain responses reflect the processing of the specific visual features that modulate categorization behavior—the “what”. The N170 is the earliest Event-Related Potential (ERP) that preferentially responds to faces. Here, we demonstrate that a paradigmatic shift is necessary to interpret the N170 as the product of an information processing network that dynamically codes and transfers face features across hemispheres, rather than as a local stimulus-driven event. Reverse-correlation methods coupled with information-theoretic analyses revealed that visibility of the eyes influences face detection behavior. The N170 initially reflects coding of the behaviorally relevant eye contralateral to the sensor, followed by a causal communication of the other eye from the other hemisphere. These findings demonstrate that the deceptively simple N170 ERP hides a complex network information processing mechanism involving initial coding and subsequent cross-hemispheric transfer of visual features. PMID:27550865

  14. 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.

  15. 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

  16. 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.

  17. 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.

  18. Intermanual transfer and bilateral cortical plasticity is maintained in older adults after skilled motor training with simple and complex tasks

    PubMed Central

    Dickins, Daina S. E.; Sale, Martin V.; Kamke, Marc R.

    2015-01-01

    Intermanual transfer refers to the phenomenon whereby unilateral motor training induces performance gains in both the trained limb and in the opposite, untrained limb. Evidence indicates that intermanual transfer is attenuated in older adults following training on a simple ballistic movement task, but not after training on a complex task. This study investigated whether differences in plasticity in bilateral motor cortices underlie these differential intermanual transfer effects in older adults. Twenty young (<35 years-old) and older adults (>65 years) trained on a simple (repeated ballistic thumb abduction) and complex (sequential finger-thumb opposition) task in separate sessions. Behavioral performance was used to quantify intermanual transfer between the dominant (trained) and non-dominant (untrained) hands. The amplitude of motor-evoked potentials induced by single pulse transcranial magnetic stimulation was used to investigate excitability changes in bilateral motor cortices. Contrary to predictions, both age groups exhibited performance improvements in both hands after unilateral skilled motor training with simple and complex tasks. These performance gains were accompanied by bilateral increases in cortical excitability in both groups for the simple but not the complex task. The findings suggest that advancing age does not necessarily influence the capacity for intermanual transfer after training with the dominant hand. PMID:25999856

  19. 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.

  20. [Comparison of group transfer, inner sphere and outer sphere electron transfer mechanisms of organometallic complexes: Progress report

    SciTech Connect

    Atwood, J.

    1990-12-31

    We have constructed an infrared stopped-flow spectrophotometer and initiated a study of the mechanisms of reactions that involve a change in the oxidation state of organometallic complexes. In this summary we highlight our results on reactions (1) that formally involve exchange of a charged species between two metal carbonyl anions, (2) that involve addition of an electron to, or removal of an electron from organometallic complexes that contain a metal-metal bond, and (3) between coordination complexes and metal carbonyl anions.

  1. (Comparison of group transfer, inner sphere and outer sphere electron transfer mechanisms of organometallic complexes: Progress report)

    SciTech Connect

    Atwood, J.

    1990-01-01

    We have constructed an infrared stopped-flow spectrophotometer and initiated a study of the mechanisms of reactions that involve a change in the oxidation state of organometallic complexes. In this summary we highlight our results on reactions (1) that formally involve exchange of a charged species between two metal carbonyl anions, (2) that involve addition of an electron to, or removal of an electron from organometallic complexes that contain a metal-metal bond, and (3) between coordination complexes and metal carbonyl anions.

  2. Applying complexity theory: a review to inform evaluation design.

    PubMed

    Walton, Mat

    2014-08-01

    Complexity theory has increasingly been discussed and applied within evaluation literature over the past decade. This article reviews the discussion and use of complexity theory within academic journal literature. The aim is to identify the issues to be considered when applying complexity theory to evaluation. Reviewing 46 articles, two groups of themes are identified. The first group considers implications of applying complexity theory concepts for defining evaluation purpose, scope and units of analysis. The second group of themes consider methodology and method. Results provide a starting point for a configuration of an evaluation approach consistent with complexity theory, whilst also identifying a number of design considerations to be resolved within evaluation planning.

  3. 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.

  4. Quantitative calculations of fluorescence polarization and absorption anisotropy kinetics of double- and triple-chromophore complexes with energy transfer.

    PubMed Central

    Demidov, A A

    1994-01-01

    A new method is presented for calculation of the fluorescence depolarization and kinetics of absorption anisotropy for molecular complexes with a limited number of chromophores. The method considers absorption and emission of light by both chromophores, and also energy transfer between them, with regard to their mutual orientations. The chromophores in each individual complex are rigidly positioned. The complexes are randomly distributed and oriented in space, and there is no energy transfer between them. The new "practical" formula for absorption anisotropy and fluorescence depolarization kinetics, P(t) = [3B(t) - 1 + 2A(t)]/[3 + B(t) + 4A(t)], is derived both for double- and triple-chromophore complexes with delta-pulse excitation. The parameter B(t) is given by (a) B(t) = cos2(theta) for double-chromophore complexes, and (b) B(t) = q12(t)cos2(theta 12) + q13(t)-cos2(theta 13) + q23(t)cos2(theta 23) for triple-chromophore complexes, where q12(t) + q13(t) + q23(t) = 1. Here theta ij are the angles between the chromophore transition dipole moments in the individual molecular complex. The parameters qij(t) and A(t) are dependent on chromophore spectroscopic features and on the rates of energy transfer. PMID:7696461

  5. 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.…

  6. 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…

  7. 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).

  8. Information transfer with rate-modulated Poisson processes: a simple model for nonstationary stochastic resonance.

    PubMed

    Goychuk, I

    2001-08-01

    Stochastic resonance in a simple model of information transfer is studied for sensory neurons and ensembles of ion channels. An exact expression for the information gain is obtained for the Poisson process with the signal-modulated spiking rate. This result allows one to generalize the conventional stochastic resonance (SR) problem (with periodic input signal) to the arbitrary signals of finite duration (nonstationary SR). Moreover, in the case of a periodic signal, the rate of information gain is compared with the conventional signal-to-noise ratio. The paper establishes the general nonequivalence between both measures notwithstanding their apparent similarity in the limit of weak signals.

  9. Information transfer with rate-modulated Poisson processes: A simple model for nonstationary stochastic resonance

    NASA Astrophysics Data System (ADS)

    Goychuk, Igor

    2001-08-01

    Stochastic resonance in a simple model of information transfer is studied for sensory neurons and ensembles of ion channels. An exact expression for the information gain is obtained for the Poisson process with the signal-modulated spiking rate. This result allows one to generalize the conventional stochastic resonance (SR) problem (with periodic input signal) to the arbitrary signals of finite duration (nonstationary SR). Moreover, in the case of a periodic signal, the rate of information gain is compared with the conventional signal-to-noise ratio. The paper establishes the general nonequivalence between both measures notwithstanding their apparent similarity in the limit of weak signals.

  10. 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.

  11. Synthesis and spectroscopic properties of platinum(II) terpyridine complexes having an arylborane charge transfer unit.

    PubMed

    Sakuda, Eri; Funahashi, Akiko; Kitamura, Noboru

    2006-12-25

    Synthesis, redox, spectroscopic, and photophysical properties of a new class of Pt(II) complexes of the type [PtLnCl]+ are reported, where Ln is 4'-phenyl(dimesitylboryl)-2,2':6',2"-terpyridine (L1) or 4'-duryl(dimesitylboryl)-2,2':6',2"-terpyridine (L2). The free L1 or L2 ligand in CH3CN shows the absorption band responsible for intramolecular charge transfer (CT) from the pi-orbital of the aryl group in L1 or L2 (pi(aryl)) to the vacant p-orbital on the boron atom (p(B)), in addition to pipi* absorption in the 2,2':6',2"-terpyridine (tpy) unit. In particular, the L1 ligand shows an intense CT absorption band as compared with L2. Such intramolecular pi(aryl)-p(B) CT interactions in L1 give rise to large influences on the redox, spectroscopic, and photophysical properties of [PtL1Cl]+. In practice, [PtL1Cl]+ shows strong room-temperature emission in CHCl3 with the quantum yield and lifetime of 0.011 and 0.6 micros, respectively, which has been explained by synergetic effects of Pt(II)-to-L1 MLCT and pi(aryl)-p(B) CT interactions on the electronic structures of the complex. In the case of [PtL2Cl]+, the dihedral angle between the planes produced by the tpy and duryl(dimesitylborane) groups is very large (84 degrees ) as compared with that between the tpy and phenyl(dimesitylborane) units in [PtL1Cl]+ (26-39 degrees ), which disturbs electron communication between the Pt(II)-tpy and arylborane units in [PtL2Cl]+. Thus, [PtL2Cl]+ is nonemissive at room temperature. The important roles of the synergetic CT interactions in the excited-state properties of the [PtL1Cl]+ complex are shown clearly by emission quenching of the complex by a fluoride ion. The X-ray crystal structure of [PtL1Cl]+ is also reported.

  12. 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.

  13. Public information influences sperm transfer to females in sailfin molly males.

    PubMed

    Nöbel, Sabine; Witte, Klaudia

    2013-01-01

    In animals, including humans, the social environment can serve as a public information network in which individuals can gather public information about the quality of potential mates by observing conspecifics during sexual interactions. The observing individual itself is also a part of this information network. When recognized by the observed conspecifics as an audience, his/her presence could influence the sexual interaction between those individuals, because the observer might be considered as a potential mate or competitor. One of the most challenging questions in sexual selection to date is how the use of public information in the context of mate choice is linked to the fitness of individuals. Here, we could show that public information influences mate-choice behaviour in sailfin molly males, Poecilia latipinna, and influences the amount of sperm males transfer to a female partner. In the presence of an audience male, males spent less time with the previously preferred, larger of two females and significantly more time with the previously non-preferred, smaller female. When males could physically interact with a female and were faced with an audience male, three audience females or no audience, males transferred significantly more sperm to a female partner in the presence of an audience male than with female audience or no audience and spent less time courting his female partner. This is the first study showing that public information use turns into fitness investment, which is the crucial factor to understand the role of public information in the dynamic processes in sexual selection.

  14. 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

  15. 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

  16. Analytical study for the charge-transfer complexes of rosuvastatin calcium with π-acceptors.

    PubMed

    Alzoman, Nourah Z; Sultan, Maha A; Maher, Hadir M; Alshehri, Mona M; Wani, Tanveer A; Darwish, Ibrahim A

    2013-07-03

    Studies were carried out to investigate the charge-transfer (CT) reaction of ROS-Ca, as a n-electron donor with various p-acceptors: tetracyanoethylene, p-chloranilic acid, 2,3-dichloro-5,6-dicyano-1,4-benzoquinone, 2,3,5,6-tetrabromo-1,4-benzoquinone, 1,3,5-trinitrobenzene, 2,3,5,6-tetrachloro-1,4-benzoquinone, 7,7,8,8-tetracyano-quinodimethane, and 2,4,7-trinitro-9-fluorenone. Different colored CT complexes were obtained. The reaction mechanism and site of interaction were determined by ultraviolet-visible spectrophotometric techniques and computational molecular modeling. The formation of the colored complexes was utilized in the development of simple, rapid and accurate spectrophotometric methods for the determination of ROS-Ca. Under the optimum reaction conditions, linear relationships with good correlation coefficients (0.9984-0.9995) were found between the absorbances and the concentrations of ROS-Ca in the range of 2-200 mg mL⁻¹. The limits of detection ranged from 0.41 to 12.24 mg mL⁻¹. No interference could be observed from the additives commonly present in the tablets or from the drugs that are co-formulated with ROS-Ca in its combined formulations. The methods were successfully applied to the analysis of tablets with good accuracy and precision; the recovery percentages ranged from 99.54-100.46 ± 1.58-1.82%. The results were compared favorably with the reported method. The proposed methods are practical and valuable for routine application in quality control laboratories for determination of ROS-Ca in its bulk form and tablets.

  17. Mechanistic studies of the transfer dehydrogenation of cyclooctane catalyzed by iridium bis(phosphinite) p-XPCP pincer complexes.

    PubMed

    Göttker-Schnetmann, Inigo; Brookhart, Maurice

    2004-08-01

    Reaction of bis(phosphinite) PCP iridium pincer complexes (p-XPCP)IrHCl (5a-f) [X = MeO (5a), Me (5b), H (5c), F (5d), C(6)F(5) (5e), Ar(F)(= 3,5-bis(trifluoromethyl)phenyl) (5f)] with NaOtBu in neat cyclooctane (COA) generates 1:1 mixtures of the respective (p-XPCP)IrH(2) complexes 4a-f and the cyclooctene (COE) olefin complexes (p-XPCP)Ir(COE) (6a-f) at 23 degrees C. At higher temperatures, complexes 4 and 6 are equilibrated because of the degenerate transfer dehydrogenation of COA with free COE (6 + COA right harpoon over left harpoon 4 + 2COE), as was shown by temperature-dependent equilibrium constants and spin saturation transfer experiments at 80 degrees C. At this temperature, the COE complexes 6 exchange with free COE on the NMR time scale with the more electron-deficient complexes 6 exchanging COE faster. The exchange is dissociative and zero order in [COE]. Further analysis reveals that the stoichiometric hydrogenation of COE by complex 4f, and thus the separated back reaction 4f + 2COE --> 6f + COA proceeds at temperatures as low as -100 degrees C with the intermediacy of two isomeric complexes (p-Ar(F)PCP)Ir(H)(2)(COE) (8f, 8f'). COE deuteration with the perdeuterated complex 4f-d(38) at -100 degrees C results in hydrogen incorporation into the hydridic sites of complexes 8f,8f'-d(38) but not in the hydridic sites of complex 4f-d(38), thus rendering COE migratory insertion in complexes 8f,8f' reversible and COE coordination by complex 4f rate-determining for the overall COE deuteration.

  18. 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:...

  19. Report of a Planning Conference for Solar Technology Information Transfer in Georgia (Atlanta, Georgia, July 24-25, 1978).

    ERIC Educational Resources Information Center

    Aldridge, Mark C., Ed.

    A summary of the deliberations of the Georgia planning conference of the Solar Technology Transfer Program is presented in this report. Topic areas include background information on the Georgia conference and a summary of the discussions and recommendations dealing with solar information transfer within state systems and the need for greater…

  20. Transference of Traditional Versus Complex Strength and Power Training to Sprint Performance

    PubMed Central

    Loturco, Irineu; Tricoli, Valmor; Roschel, Hamilton; Nakamura, Fabio Yuzo; Cal Abad, Cesar Cavinato; Kobal, Ronaldo; Gil, Saulo; González-Badillo, Juan José

    2014-01-01

    The purpose of this study was to determine the effects of two different strength-power training models on sprint performance. Forty-eight soldiers of the Brazilian brigade of special operations with at least one year of army training experience were divided into a control group (CG: n = 15, age: 20.2 ± 0.7 years, body height: 1.74 ± 0.06 m, and body mass: 66.7 ± 9.8 kg), a traditional training group (TT: n = 18, age: 20.1 ± 0.7 years, body height: 1.71 ± 0.05 m, and body mass: 64.2 ± 4.7 kg), and a complex training group (CT: n = 15, age: 20.3 ± 0.8 years, body height: 1.71 ± 0.07 m; and body mass: 64.0 ± 8.8 kg). Maximum strength (25% and 26%), CMJ height (36% and 39%), mean power (30% and 35%) and mean propulsive power (22% and 28%) in the loaded jump squat exercise, and 20-m sprint speed (16% and 14%) increased significantly (p≤0.05) following the TT and CT, respectively. However, the transfer effect coefficients (TEC) of strength and power performances to 20-m sprint performance following the TT were greater than the CT throughout the 9-week training period. Our data suggest that TT is more effective than CT to improve sprint performance in moderately trained subjects. PMID:25114753

  1. Influence of tailored MLI for complex surface geometries on heat transfer

    NASA Astrophysics Data System (ADS)

    Neumann, H.; Mayrhofer, R.; Richter, T.

    2015-12-01

    Complex, non-developable surfaces require a tailored multi-layer insulation (MLI) for lowest heat load. The most experiments showing the heat transfer through MLI are performed under quasi-ideal conditions determining the principle insulation quality. But the surface to be insulated in real cryostats implies feed-throughs and other non-developable surface parts. The thermal performance of MLI is degraded significantly at cutting points. To investigate this degrading effect a LN2-filled cylinder with a diameter of 219 mm and a length of 1820 mm was insulated with MLI and the heat load was measured by means of calorimetry. In addition the heat load to an insulated cylinder with eighteen branches was measured. Both cylinders have the same surface of 1.37 m2 for a comparison of the results. This article describes the experiments with different ways of tailoring the MLI for the cylinder with branches and discusses their results. It was shown that the cutting points at the branches have a significant degrading influence on the thermal performance of MLI.

  2. Side chain effects in reactions of the potassium-tyrosine charge transfer complex

    NASA Astrophysics Data System (ADS)

    da Silva, F. Ferreira; Meneses, G.; Ingólfsson, O.; Limão-Vieira, P.

    2016-10-01

    Fragmentation of transient negative ions of tyrosine formed through electron transfer in collisions with neutral potassium atoms is presented in the collision energy range from 30 to 75 eV. At low collision energies the dominating side chain channel observed corresponds to the cleavage of the bond from the para-position of the phenyl ring to the β-C of the remaining moiety, but cleavage of the Cαsbnd Cβ bond is also observed. Further fragments are formed through cleavage of the Cα bond to the carbonyl group, through decomposition of the carboxyl group or through significant decomposition of the backbone. The dehydrogenated molecular anion is also observed with appreciable intensity. These results are discussed in the context of earlier studies on dissociative electron attachment to tyrosine and other amino acids, as well as within the role of the side chain in electron induced decomposition of this aromatic amino acid. Stabilization of the temporary molecular anion in the transient collision complex is discussed and we argue that this may have significant influence on the branching ratios observed.

  3. 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

  4. Spectral Transfer Learning Using Information Geometry for a User-Independent Brain-Computer Interface

    PubMed Central

    Waytowich, Nicholas R.; Lawhern, Vernon J.; Bohannon, Addison W.; Ball, Kenneth R.; Lance, Brent J.

    2016-01-01

    Recent advances in signal processing and machine learning techniques have enabled the application of Brain-Computer Interface (BCI) technologies to fields such as medicine, industry, and recreation; however, BCIs still suffer from the requirement of frequent calibration sessions due to the intra- and inter-individual variability of brain-signals, which makes calibration suppression through transfer learning an area of increasing interest for the development of practical BCI systems. In this paper, we present an unsupervised transfer method (spectral transfer using information geometry, STIG), which ranks and combines unlabeled predictions from an ensemble of information geometry classifiers built on data from individual training subjects. The STIG method is validated in both off-line and real-time feedback analysis during a rapid serial visual presentation task (RSVP). For detection of single-trial, event-related potentials (ERPs), the proposed method can significantly outperform existing calibration-free techniques as well as outperform traditional within-subject calibration techniques when limited data is available. This method demonstrates that unsupervised transfer learning for single-trial detection in ERP-based BCIs can be achieved without the requirement of costly training data, representing a step-forward in the overall goal of achieving a practical user-independent BCI system. PMID:27713685

  5. Isonitrile iron(II) complexes with chiral N2P2 macrocycles in the enantioselective transfer hydrogenation of ketones.

    PubMed

    Bigler, Raphael; Mezzetti, Antonio

    2014-12-19

    Bis(isonitrile) iron(II) complexes bearing a C2-symmetric N2P2 macrocyclic ligand, which are easily prepared from the corresponding bis(acetonitrile) analogue, catalyze the asymmetric transfer hydrogenation (ATH) of a broad scope of ketones in excellent yields (up to 98%) and with high enantioselectivity (up to 91% ee).

  6. Ultrafast inter-ionic charge transfer of transition-metal complexes mapped by femtosecond X-ray powder diffraction

    SciTech Connect

    Freyer, Benjamin; Zamponi, Flavio; Juve, Vincent; Stingl, Johannes; Woerner, Michael; Elsaesser, Thomas; Chergui, Majed

    2013-04-14

    The transient electronic and molecular structure arising from photoinduced charge transfer in transition metal complexes is studied by X-ray powder diffraction with a 100 fs temporal and atomic spatial resolution. Crystals containing a dense array of Fe(II)-tris(bipyridine) ([Fe(bpy){sub 3}]{sup 2+}) complexes and their PF{sub 6}{sup -} counterions display pronounced changes of electron density that occur within the first 100 fs after two-photon excitation of a small fraction of the [Fe(bpy){sub 3}]{sup 2+} complexes. Transient electron density maps derived from the diffraction data reveal a transfer of electronic charge from the Fe atoms and-so far unknown-from the PF{sub 6}{sup -} counterions to the bipyridine units. Such charge transfer (CT) is connected with changes of the inter-ionic and the Fe-bipyridine distances. An analysis of the electron density maps demonstrates the many-body character of charge transfer which affects approximately 30 complexes around a directly photoexcited one. The many-body behavior is governed by the long-range Coulomb forces in the ionic crystals and described by the concept of electronic polarons.

  7. Photoinduced singlet charge transfer in a ruthenium(II) perylene-3,4:9,10-bis(dicarboximide) complex.

    PubMed

    Gunderson, Victoria L; Krieg, Elisha; Vagnini, Michael T; Iron, Mark A; Rybtchinski, Boris; Wasielewski, Michael R

    2011-06-16

    Elucidation of photoinduced charge transfer behavior in organic dye/metal hybrids is important for developing photocatalytic systems for solar energy conversion. We report the synthesis and photophysical characterization of a perylene-3,4:9,10-bis(dicarboximide) (PDI)-ruthenium(II) complex, bis-PDI-2,2'-bipyridineRu(II)Cl(2)(CN(t)butyl)(2), which has favorable energetics, ΔG(CS) ≈ -1.0 eV, for singlet electron transfer from the Ru complex to PDI. Time-resolved optical spectroscopy reveals that upon selective photoexcitation of PDI, ultrafast charge transfer (<150 fs) from the Ru complex to (1*)PDI generates the Ru(III)-PDI(-•) ion pair. The resulting vibrationally hot Ru(III)-PDI(-•) ion pair exhibits fast relaxation (τ = 3.9 ps) and charge recombination (τ(CR) = 63 ps). Our experimental and computational (DFT and TDDFT) studies show that energy-preserving photodriven singlet electron transfer can dominate in properly designed organic dye/metal complexes, making them of particular interest for use in artificial photosynthetic systems for solar fuels formation. PMID:21598951

  8. 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...

  9. Spectroscopic studies and molecular orbital calculations of charge transfer complexation between 3,5-dimethylpyrazole with DDQ in acetonitrile

    NASA Astrophysics Data System (ADS)

    Habeeb, Moustafa M.; Al-Attas, Amirah S.; Al-Raimi, Doaa S.

    2015-05-01

    Charge transfer (CT) interaction between 3,5-dimethylpyrazole (DMP) with the π-acceptor 2,3-dichloro-5,6-dicyano-p-benzoquinon (DDQ) has been investigated spectrophotometrically in acetonitrile (AN). Simultaneous reddish brown color has been observed upon mixing donor with acceptor solutions attributing to CT complex formation. The electronic spectra of the formed complex exhibited multi-charge transfer bands at 429, 447, 506, 542 and 589 nm, respectively. Job's method of continuous variations and spectrophotometric titration methods confirmed the formation of the studied complex in 1:2 ratio between DMP and DDQ. Benesi-Hildebrand equation has been applied to calculate the stability constant of the formed complex where it recorded high value supporting formation of stable complex. Molecular orbital calculations using MM2 method and GAMESS (General Atomic and Molecular Electronic Structure System) interface computations as a package of ChemBio3D Ultra12 software were carried out for more analysis of the formed complex in the gas phase. The computational analysis included energy minimisation, stabilisation energy, molecular geometry, Mullikan charges, molecular electrostatic potential (MEP) surfaces of reactants and complex as well as characterization of the higher occupied molecular orbitals (HOMO) and lower unoccupied molecular orbitals (LUMO) surfaces of the complex. A good consistency between experimental and theoretical results has been recorded.

  10. Stochastic information transfer from cochlear implant electrodes to auditory nerve fibers

    NASA Astrophysics Data System (ADS)

    Gao, Xiao; Grayden, David B.; McDonnell, Mark D.

    2014-08-01

    Cochlear implants, also called bionic ears, are implanted neural prostheses that can restore lost human hearing function by direct electrical stimulation of auditory nerve fibers. Previously, an information-theoretic framework for numerically estimating the optimal number of electrodes in cochlear implants has been devised. This approach relies on a model of stochastic action potential generation and a discrete memoryless channel model of the interface between the array of electrodes and the auditory nerve fibers. Using these models, the stochastic information transfer from cochlear implant electrodes to auditory nerve fibers is estimated from the mutual information between channel inputs (the locations of electrodes) and channel outputs (the set of electrode-activated nerve fibers). Here we describe a revised model of the channel output in the framework that avoids the side effects caused by an "ambiguity state" in the original model and also makes fewer assumptions about perceptual processing in the brain. A detailed comparison of how different assumptions on fibers and current spread modes impact on the information transfer in the original model and in the revised model is presented. We also mathematically derive an upper bound on the mutual information in the revised model, which becomes tighter as the number of electrodes increases. We found that the revised model leads to a significantly larger maximum mutual information and corresponding number of electrodes compared with the original model and conclude that the assumptions made in this part of the modeling framework are crucial to the model's overall utility.

  11. Synthesis, characterization, and application of vanadium-salan complexes in oxygen transfer reactions.

    PubMed

    Adão, Pedro; Costa Pessoa, João; Henriques, Rui T; Kuznetsov, Maxim L; Avecilla, Fernando; Maurya, Mannar R; Kumar, Umesh; Correia, Isabel

    2009-04-20

    We report the synthesis and characterization of several chiral salen- and salan-type ligands and their vanadium complexes, which are derived from salicylaldehyde or salicylaldehyde derivatives and chiral diamines (1R,2R-diaminocyclohexane, 1S,2S-diaminocyclohexane, and 1S,2S-diphenylethylenediamine). The structures of H(2)sal(R,R-chan)(2+) x 2 Cl(-) x (CH(3))(2)CHOH x H(2)O (1c; H(2)sal(R,R-chan) = N,N'-salicyl-R,R-cyclohexanediaminium), Etvan(S,S-chen) (3c; Etvan(S,S-chen) = N,N'-3-ethoxy-salicylidene-S,S-cyclohexanediiminato), and naph(R,R-chen) (6c; naph(R,R-chen) = N,N'-naphthylidene-R,R-cyclohexanediiminato) were determined by single-crystal X-ray diffraction. The corresponding vanadium(IV) complexes and several other new complexes involving different salicylaldehyde-type precursors were prepared and characterized in the solid state and in solution by spectroscopic techniques: UV-vis, circular dichroism, electron paramagnetic resonance, and (51)V NMR, which provide information on the coordination geometry. The salan complexes oxidize in organic solvents to V(V) species, and this process was also studied using spectroscopic techniques. Single crystals suitable for X-ray diffraction were obtained for [{V(V)O[sal(S,S-dpan)]}(2)(mu-O)] x H(2)O x 2(CH(3))(2)CHOH (14c; sal(S,S-dpan) = N,N'-salicyl-S,S-diphenylethylenediaminato) and [{V(V)O[t-Busal(R,R-chan)]}(2)(mu-O)] x 2 (CH(3))(2)CHOH (15c), both containing an OV(V)(mu-O)V(V)O moiety (V(2)O(3)(4+) core) with tetradentate ligands and one mu-oxo bridge. Both structures are the first examples of dinuclear vanadium complexes involving the V(V)(2)O(3)(4+) core with tetradentate ligands, the configuration of the V(2)O(3) unit being twist-angular. The V-salen and V-salan complexes are tested as catalysts in the oxidation of styrene, cyclohexene, cumene, and methyl phenyl sulfide with H(2)O(2) and t-BuOOH as oxidants. Overall, the V-salan complexes show higher activity and normally better selectivity in alkene oxidation

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

    PubMed

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

    2016-06-01

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

  13. 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 ...

  14. 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 ...

  15. Highly efficient energy transfer from a carbonyl carotenoid to chlorophyll a in the main light harvesting complex of Chromera velia.

    PubMed

    Durchan, Milan; Keşan, Gürkan; Slouf, Václav; Fuciman, Marcel; Staleva, Hristina; Tichý, Josef; Litvín, Radek; Bína, David; Vácha, František; Polívka, Tomáš

    2014-10-01

    We report on energy transfer pathways in the main light-harvesting complex of photosynthetic relative of apicomplexan parasites, Chromera velia. This complex, denoted CLH, belongs to the family of FCP proteins and contains chlorophyll (Chl) a, violaxanthin, and the so far unidentified carbonyl carotenoid related to isofucoxanthin. The overall carotenoid-to-Chl-a energy transfer exhibits efficiency over 90% which is the largest among the FCP-like proteins studied so far. Three spectroscopically different isofucoxanthin-like molecules were identified in CLH, each having slightly different energy transfer efficiency that increases from isofucoxanthin-like molecules absorbing in the blue part of the spectrum to those absorbing in the reddest part of spectrum. Part of the energy transfer from carotenoids proceeds via the ultrafast S2 channel of both the violaxanthin and isofucoxanthin-like carotenoid, but major energy transfer pathway proceeds via the S1/ICT state of the isofucoxanthin-like carotenoid. Two S1/ICT-mediated channels characterized by time constants of ~0.5 and ~4ps were found. For the isofucoxanthin-like carotenoid excited at 480nm the slower channel dominates, while those excited at 540nm employs predominantly the fast 0.5ps channel. Comparing these data with the excited-state properties of the isofucoxanthin-like carotenoid in solution we conclude that, contrary to other members of the FCP family employing carbonyl carotenoids, CLH complex suppresses the charge transfer character of the S1/ICT state of the isofucoxanthin-like carotenoid to achieve the high carotenoid-to-Chl-a energy transfer efficiency.

  16. Optimal thermal bath for robust excitation energy transfer in disordered light-harvesting complex 2 of purple bacteria

    NASA Astrophysics Data System (ADS)

    Cleary, Liam; Cao, Jianshu

    2013-12-01

    The existence of an optimal thermal bath to facilitate robust energy transfer between the spectrally separated B800 and B850 rings in light-harvesting complex 2 (LH2) of purple bacteria is investigated via the multichromophoric Förster theory. Due to the inherent energy bias between the two rings, the energy transfer rate from B800 to B850 is maximized as a function of the bath coupling strength, establishing an optimization criterion. Critically, upon inclusion of energetic disorder, this maximum is averaged out. However, noting the distribution of transfer rates, we find that the bath coupling strength can yield a minimal dispersion for the rate distribution, i.e. a maximum ratio of mean to standard deviation, thus achieving maximum energy transfer robust to the effects of static disorder.

  17. Transfer of molecular recognition information from DNA nanostructures to gold nanoparticles

    NASA Astrophysics Data System (ADS)

    Edwardson, Thomas G. W.; Lau, Kai Lin; Bousmail, Danny; Serpell, Christopher J.; Sleiman, Hanadi F.

    2016-02-01

    DNA nanotechnology offers unparalleled precision and programmability for the bottom-up organization of materials. This approach relies on pre-assembling a DNA scaffold, typically containing hundreds of different strands, and using it to position functional components. A particularly attractive strategy is to employ DNA nanostructures not as permanent scaffolds, but as transient, reusable templates to transfer essential information to other materials. To our knowledge, this approach, akin to top-down lithography, has not been examined. Here we report a molecular printing strategy that chemically transfers a discrete pattern of DNA strands from a three-dimensional DNA structure to a gold nanoparticle. We show that the particles inherit the DNA sequence configuration encoded in the parent template with high fidelity. This provides control over the number of DNA strands and their relative placement, directionality and sequence asymmetry. Importantly, the nanoparticles produced exhibit the site-specific addressability of DNA nanostructures, and are promising components for energy, information and biomedical applications.

  18. Solution structure of barley lipid transfer protein complexed with palmitate. Two different binding modes of palmitate in the homologous maize and barley nonspecific lipid transfer proteins.

    PubMed Central

    Lerche, M. H.; Poulsen, F. M.

    1998-01-01

    The structure of a nonspecific lipid transfer protein from barley (ns-LTPbarley) in complex with palmitate has been determined by NMR spectroscopy. The structure has been compared to the structure of ns-LTPbarley in the absence of palmitate, to the structure of ns-LTPbarley in complex with palmitoyl coenzyme A, to the structure of ns-LTPmaize in its free form, and to the maize protein complexed with palmitate. Binding of palmitate only affects the structure of ns-LTPbarley moderately in contrast to the binding of palmitoyl coenzyme A, which leads to a considerable expansion of the protein. The modes of binding palmitate to the maize and barley protein are different. Although in neither case there are major conformational changes in the protein, the orientation of the palmitate in the two proteins is exactly opposite. PMID:9865943

  19. Public service communications satellite. [health, education, safety and information transfer applications

    NASA Technical Reports Server (NTRS)

    Wolff, E. A.

    1978-01-01

    Health, education, public safety, and information transfer applications of public service communications satellites are discussed with particular attention to the use of communications satellites to improve rural health delivery. Health-care communications requirements are summarized. The communications system concept involves small inexpensive stationary, portable, and moving ground terminals which will provide communications between any two points in the U.S. with both fixed and moving terminals on a continuous 24-hour basis. User requirements, wavebands, and privacy techniques are surveyed.

  20. Transfer of entangled state, entanglement swapping and quantum information processing via the Rydberg blockade

    NASA Astrophysics Data System (ADS)

    Deng, Li; Chen, Ai-Xi; Zhang, Jian-Song

    2011-11-01

    We provide a scheme with which the transfer of the entangled state and the entanglement swapping can be realized in a system of neutral atoms via the Rydberg blockade. Our idea can be extended to teleport an unknown atomic state. According to the latest theoretical research of the Rydberg excitation and experimental reports of the Rydberg blockade effect in quantum information processing, we discuss the experimental feasibility of our scheme.

  1. Telecommunications Information Network: A Model for On-Demand Transfer of Medical Information. Final Report.

    ERIC Educational Resources Information Center

    Lorenzi, Nancy M.; And Others

    This report summarizes the third phase of the Telecommunications Information Network (TIN), which provides a telecommunications link between four remote southwest Ohio hospitals and the University of Cincinnati Medical Center, thereby reducing the isolation of healthcare providers at the remote hospitals. A description of the system explains the…

  2. Telecommunications Information Network: A Model for On-Demand Transfer of Medical Information. Annual Report.

    ERIC Educational Resources Information Center

    Lorenzi, Nancy M.; And Others

    This report describes and evaluates the first year of a demonstration project to develop an on-demand telecommunications network linking four remote hospitals in southwestern Ohio to the University of Cincinnati Medical Center. The Telecommunications Information Network (TIN) is designed to allow health care professionals at those hospitals to…

  3. Knowledge-based navigation of complex information spaces

    SciTech Connect

    Burke, R.D.; Hammond, K.J.; Young, B.C.

    1996-12-31

    While the explosion of on-line information has brought new opportunities for finding and using electronic data, it has also brought to the forefront the problem of isolating useful information and making sense of large multi-dimension information spaces. We have built several developed an approach to building data {open_quotes}tour guides,{close_quotes} called FINDME systems. These programs know enough about an information space to be able to help a user navigate through it. The user not only comes away with items of useful information but also insights into the structure of the information space itself. In these systems, we have combined ideas of instance-based browsing, structuring retrieval around the critiquing of previously-retrieved examples, and retrieval strategies, knowledge-based heuristics for finding relevant information. We illustrate these techniques with several examples, concentrating especially on the RENTME system, a FINDME system for helping users find suitable rental apartments in the Chicago metropolitan area.

  4. 100% Classification Accuracy Considered Harmful: The Normalized Information Transfer Factor Explains the Accuracy Paradox

    PubMed Central

    Valverde-Albacete, Francisco J.; Peláez-Moreno, Carmen

    2014-01-01

    The most widely spread measure of performance, accuracy, suffers from a paradox: predictive models with a given level of accuracy may have greater predictive power than models with higher accuracy. Despite optimizing classification error rate, high accuracy models may fail to capture crucial information transfer in the classification task. We present evidence of this behavior by means of a combinatorial analysis where every possible contingency matrix of 2, 3 and 4 classes classifiers are depicted on the entropy triangle, a more reliable information-theoretic tool for classification assessment. Motivated by this, we develop from first principles a measure of classification performance that takes into consideration the information learned by classifiers. We are then able to obtain the entropy-modulated accuracy (EMA), a pessimistic estimate of the expected accuracy with the influence of the input distribution factored out, and the normalized information transfer factor (NIT), a measure of how efficient is the transmission of information from the input to the output set of classes. The EMA is a more natural measure of classification performance than accuracy when the heuristic to maximize is the transfer of information through the classifier instead of classification error count. The NIT factor measures the effectiveness of the learning process in classifiers and also makes it harder for them to “cheat” using techniques like specialization, while also promoting the interpretability of results. Their use is demonstrated in a mind reading task competition that aims at decoding the identity of a video stimulus based on magnetoencephalography recordings. We show how the EMA and the NIT factor reject rankings based in accuracy, choosing more meaningful and interpretable classifiers. PMID:24427282

  5. Charge-transfer complex formation in gelation: the role of solvent molecules with different electron-donating capacities.

    PubMed

    Basak, Shibaji; Bhattacharya, Sumantra; Datta, Ayan; Banerjee, Arindam

    2014-05-01

    A naphthalenediimide (NDI)-based synthetic peptide molecule forms gels in a particular solvent mixture (chloroform/aromatic hydrocarbon, 4:1) through charge-transfer (CT) complex formation; this is evident from the corresponding absorbance and fluorescence spectra at room temperature. Various aromatic hydrocarbon based solvents, including benzene, toluene, xylene (ortho, meta and para) and mesitylene, have been used for the formation of the CT complex. The role of different solvent molecules with varying electron-donation capacities in the formation of CT complexes has been established through spectroscopic and computational studies. PMID:24677404

  6. Fast spin information transfer between distant quantum dots using individual electrons.

    PubMed

    Bertrand, B; Hermelin, S; Takada, S; Yamamoto, M; Tarucha, S; Ludwig, A; Wieck, A D; Bäuerle, C; Meunier, T

    2016-08-01

    Transporting ensembles of electrons over long distances without losing their spin polarization is an important benchmark for spintronic devices. It usually requires injecting and probing spin-polarized electrons in conduction channels using ferromagnetic contacts or optical excitation. In parallel with this development, important efforts have been dedicated to achieving control of nanocircuits at the single-electron level. The detection and coherent manipulation of the spin of a single electron trapped in a quantum dot are now well established. Combined with the recently demonstrated control of the displacement of individual electrons between two distant quantum dots, these achievements allow the possibility of realizing spintronic protocols at the single-electron level. Here, we demonstrate that spin information carried by one or two electrons can be transferred between two quantum dots separated by a distance of 4 μm with a classical fidelity of 65%. We show that at present it is limited by spin flips occurring during the transfer procedure before and after electron displacement. Being able to encode and control information in the spin degree of freedom of a single electron while it is being transferred over distances of a few micrometres on nanosecond timescales will pave the way towards 'quantum spintronics' devices, which could be used to implement large-scale spin-based quantum information processing. PMID:27240417

  7. Fast spin information transfer between distant quantum dots using individual electrons.

    PubMed

    Bertrand, B; Hermelin, S; Takada, S; Yamamoto, M; Tarucha, S; Ludwig, A; Wieck, A D; Bäuerle, C; Meunier, T

    2016-08-01

    Transporting ensembles of electrons over long distances without losing their spin polarization is an important benchmark for spintronic devices. It usually requires injecting and probing spin-polarized electrons in conduction channels using ferromagnetic contacts or optical excitation. In parallel with this development, important efforts have been dedicated to achieving control of nanocircuits at the single-electron level. The detection and coherent manipulation of the spin of a single electron trapped in a quantum dot are now well established. Combined with the recently demonstrated control of the displacement of individual electrons between two distant quantum dots, these achievements allow the possibility of realizing spintronic protocols at the single-electron level. Here, we demonstrate that spin information carried by one or two electrons can be transferred between two quantum dots separated by a distance of 4 μm with a classical fidelity of 65%. We show that at present it is limited by spin flips occurring during the transfer procedure before and after electron displacement. Being able to encode and control information in the spin degree of freedom of a single electron while it is being transferred over distances of a few micrometres on nanosecond timescales will pave the way towards 'quantum spintronics' devices, which could be used to implement large-scale spin-based quantum information processing.

  8. Fast spin information transfer between distant quantum dots using individual electrons

    NASA Astrophysics Data System (ADS)

    Bertrand, B.; Hermelin, S.; Takada, S.; Yamamoto, M.; Tarucha, S.; Ludwig, A.; Wieck, A. D.; Bäuerle, C.; Meunier, T.

    2016-08-01

    Transporting ensembles of electrons over long distances without losing their spin polarization is an important benchmark for spintronic devices. It usually requires injecting and probing spin-polarized electrons in conduction channels using ferromagnetic contacts or optical excitation. In parallel with this development, important efforts have been dedicated to achieving control of nanocircuits at the single-electron level. The detection and coherent manipulation of the spin of a single electron trapped in a quantum dot are now well established. Combined with the recently demonstrated control of the displacement of individual electrons between two distant quantum dots, these achievements allow the possibility of realizing spintronic protocols at the single-electron level. Here, we demonstrate that spin information carried by one or two electrons can be transferred between two quantum dots separated by a distance of 4 μm with a classical fidelity of 65%. We show that at present it is limited by spin flips occurring during the transfer procedure before and after electron displacement. Being able to encode and control information in the spin degree of freedom of a single electron while it is being transferred over distances of a few micrometres on nanosecond timescales will pave the way towards ‘quantum spintronics’ devices, which could be used to implement large-scale spin-based quantum information processing.

  9. Mechanistic studies of photoinduced spin crossover and electron transfer in inorganic complexes.

    PubMed

    Zhang, Wenkai; Gaffney, Kelly J

    2015-04-21

    Electronic excited-state phenomena provide a compelling intersection of fundamental and applied research interests in the chemical sciences. This holds true for coordination chemistry, where harnessing the strong optical absorption and photocatalytic activity of compounds depends on our ability to control fundamental physical and chemical phenomena associated with the nonadiabatic dynamics of electronic excited states. The central events of excited-state chemistry can critically influence the dynamics of electronic excited states, including internal conversion (transitions between distinct electronic states) and intersystem crossing (transitions between electronic states with different spin multiplicities), events governed by nonadiabatic interactions between electronic states in close proximity to conical intersections, as well as solvation and electron transfer. The diversity of electronic and nuclear dynamics also makes the robust interpretation of experimental measurements challenging. Developments in theory, simulation, and experiment can all help address the interpretation and understanding of chemical dynamics in organometallic and coordination chemistry. Synthesis presents the opportunity to chemically engineer the strength and symmetry of the metal-ligand interactions. This chemical control can be exploited to understand the influence of electronic ground state properties on electronic excited-state dynamics. New time-resolved experimental methods and the insightful exploitation of established methods have an important role in understanding, and ideally controlling, the photophysics and photochemistry of transition metal complexes. Techniques that can disentangle the coupled motion of electrons and nuclear dynamics warrant emphasis. We present a review of electron localization dynamics in charge transfer excited states and the dynamics of photoinitiated spin crossover dynamics. Both electron localization and spin crossover have been investigated by

  10. Preferential transfer of the complete glycan is determined by the oligosaccharyltransferase complex and not by the catalytic subunit

    PubMed Central

    Castro, Olga; Movsichoff, Federico; Parodi, Armando J.

    2006-01-01

    Most eukaryotic cells show a strong preference for the transfer in vivo and in vitro of the largest dolichol-P-P-linked glycan (Glc3Man9GlcNAc2) to protein chains over that of biosynthetic intermediates that lack the full complement of glucose units. The oligosaccharyltransferase (OST) is a multimeric complex containing eight different proteins, one of which (Stt3p) is the catalytic subunit. Trypanosomatid protozoa lack an OST complex and express only this last protein. Contrary to the OST complex from most eukaryotic cells, the Stt3p subunit of these parasites transfers in cell-free assays glycans with Man7–9GlcNAc2 and Glc1–3Man9GlcNAc2 compositions at the same rate. We have replaced Saccharomyces cerevisiae Stt3p by the Trypanosoma cruzi homologue and found that the complex that is formed preferentially transfers the complete glycan both in vivo and in vitro. Thus, preference for Glc3Man9GlcNAc2 is a feature that is determined by the complex and not by the catalytic subunit. PMID:17001015

  11. Low-temperature fabrication of alkali metal-organic charge transfer complexes on cotton textile for optoelectronics and gas sensing.

    PubMed

    Ramanathan, Rajesh; Walia, Sumeet; Kandjani, Ahmad Esmaielzadeh; Balendran, Sivacarendran; Mohammadtaheri, Mahsa; Bhargava, Suresh Kumar; Kalantar-zadeh, Kourosh; Bansal, Vipul

    2015-02-01

    A generalized low-temperature approach for fabricating high aspect ratio nanorod arrays of alkali metal-TCNQ (7,7,8,8-tetracyanoquinodimethane) charge transfer complexes at 140 °C is demonstrated. This facile approach overcomes the current limitation associated with fabrication of alkali metal-TCNQ complexes that are based on physical vapor deposition processes and typically require an excess of 800 °C. The compatibility of soft substrates with the proposed low-temperature route allows direct fabrication of NaTCNQ and LiTCNQ nanoarrays on individual cotton threads interwoven within the 3D matrix of textiles. The applicability of these textile-supported TCNQ-based organic charge transfer complexes toward optoelectronics and gas sensing applications is established.

  12. Characterizing Mass Transfer of a Complex Non-aqueous Phase Liquid

    NASA Astrophysics Data System (ADS)

    McColl, C. M.; Johnson, G. R.; Brusseau, M. L.

    2004-12-01

    A series of laboratory experiments were conducted with a multiple-component, non-aqueous phase liquid (NAPL) collected from the Picillo Farm Superfund Site. Physical property analysis and compositional analysis were performed to provide initial information about the NAPL. Batch experiments were conducted to evaluate equilibrium phase-partitioning behavior. Two sets of air-stripping column studies were conducted to examine the elution behavior, mass-transfer dynamics, and mass recovery of five selected target compounds present in the NAPL mixture. Initial elution behavior of all target components appeared to be ideal, as the initial vapor-phase concentrations were similar to vapor-phase concentrations measured for the batch equilibrium experiment and those estimated using Raoult's law based calculations incorporating NAPL composition data. Air-stripping of columns containing a pool of NAPL and no porous media revealed that removal of 1,2-DCB appeared to be limited by the molecular diffusion of the compound to the NAPL-air interface. Air-stripping of NAPL distributed relatively uniformly as a residual phase within a sandy porous medium exhibited ideal behavior.

  13. Fresh look at electron-transfer mechanisms via the donor/acceptor bindings in the critical encounter complex.

    PubMed

    Rosokha, Sergiy V; Kochi, Jay K

    2008-05-01

    Seminal insights provided by the iconic R. S. Mulliken and his "charge-transfer" theory, H. Taube and his "outer/inner-sphere" mechanisms, R. A. Marcus and his "two-state non-adiabatic" theory, and N. S. Hush and his "intervalence" theory are each separately woven into the rich panoramic tapestry constituting chemical research into electron-transfer dynamics, and its mechanistic dominance for the past half century and more. In this Account, we illustrate how the simultaneous melding of all four key concepts allows sharp focus on the charge-transfer character of the critical encounter complex to evoke the latent facet of traditional electron-transfer mechanisms. To this end, we exploit the intervalence (electronic) transition that invariably accompanies the diffusive encounter of electron-rich organic donors (D) with electron-poor acceptors (A) as the experimental harbinger of the collision complex, which is then actually isolated and X-ray crystallographically established as loosely bound pi-stacked pairs of various aromatic and olefinic donor/acceptor dyads with uniform interplanar separations of r(DA) = 3.1 +/- 0.2 A. These X-ray structures, together with the spectral measurements of their intervalence transitions, lead to the pair of important electron-transfer parameters, H(DA) (electronic coupling element) versus lambdaT (reorganization energy), the ratio of which generally defines the odd-electron mobility within such an encounter complex in terms of the resonance stabilization of the donor/acceptor assembly [D, A] as opposed to the reorganization-energy penalty required for its interconversion to the electron-transfer state [D(+*), A(-*)]. We recognize the resonance-stabilization energy relative to the intrinsic activation barrier as the mechanistic binding factor, Q = 2H(DA)/lambdaT, to represent the quantitative measure of the highly variable continuum of inner-sphere/outer-sphere interactions that are possible within various types of precursor complexes

  14. Sequential energy and charge transfer processes in mixed host-guest complexes of subphthalocyanine, porphyrin and phthalocyanine chromophores.

    PubMed

    Menting, Roel; Ng, Dennis K P; Röder, Beate; Ermilov, Eugeny A

    2012-11-14

    Porphyrins, phthalocyanines and subphthalocyanines are three attractive classes of chromophores with intriguing properties making them suitable for the design of artificial photosynthetic systems. The assembly of these components by a supramolecular approach is of particular interest as it provides a facile means to build multi-chromophoric arrays with various architectures and tuneable photophysical properties. In this paper, we show the formation of mixed host-guest supramolecular complexes that consist of a β-cyclodextrin-conjugated subphthalocyanine, a tetrasulfonated porphyrin and a series of silicon(IV) phthalocyanines substituted axially with two β-cyclodextrins via different spacers. We found that the three components form supramolecular complexes held by host-guest interactions in aqueous solution. Upon excitation of the subphthalocyanine part of the complex, the excitation energy is delivered to the phthalocyanine unit via excitation energy transfer and the porphyrin chromophore acts as an energy transfer bridge enabling this process. It was shown that photo-induced charge transfer also takes place. A sequential electron transfer process from the porphyrin unit to the phthalocyanine moiety and subsequently from the subphthalocyanine moiety to the porphyrin unit takes place, and the probability of this process is controlled by the linker between β-cyclodextrin and phthalocyanine. The lifetime of the charge-separated state was found to be 1.7 ns by transient absorption spectroscopy.

  15. The formic acid-nitric acid complex: microwave spectrum, structure, and proton transfer.

    PubMed

    Mackenzie, Rebecca B; Dewberry, Christopher T; Leopold, Kenneth R

    2014-09-11

    Rotational spectra are reported for seven isotopologues of the complex HCOOH-HNO3 in a supersonic jet. The system is planar and bound by a pair of hydrogen bonds, much like the more widely studied carboxylic acid dimers. Double proton exchange interconverts the system between a pair of equivalent structures, as revealed by a splitting of the a-type spectrum that disappears when one of the hydrogen bonding protons is replaced by deuterium. The observation of relative intensities that are consistent with nuclear spin statistics in a symmetric and antisymmetric pair of tunneling states provides additional evidence for such a motion. The observed splittings in the pure rotational spectrum are 1-2 orders of magnitude smaller than those recently reported in the pure rotational spectra of several related carboxylic acid dimers. This is a curious difference, although we note that because the observed spectra do not cross the tunneling doublet, the splittings are a measure of the difference in effective rotational constants for the two states, not the tunneling frequency itself. The observed rotational constants have been used to determine an accurate vibrationally averaged structure for the complex. The two hydrogen bond lengths, 1.686(17) Å and 1.813(10) Å for the hydrogen bonds involving the HNO3 and HCOOH protons, respectively, differ by 0.127(27) Å. Likewise, the associated oxygen-oxygen distances determined for the parent species, 2.631 and 2.794 Å, differ by 0.163 Å. These results suggest that the double proton transfer is necessarily accompanied by substantial motion of the heavy atom frame, and thus this system, in principle, provides an excellent prototype for multidimensional tunneling processes. Ab initio calculations of the binding energy and the barrier height are presented. Excellent agreement between the calculated equilibrium structure and the experimental, vibrationally averaged structure suggests that the vibrational wave function is not highly

  16. Complexes of photosensitizer and CdSe/ZnS quantum dots passivated with BSA: optical properties and intracomplex energy transfer

    NASA Astrophysics Data System (ADS)

    Kuznetsova, Vera; Orlova, Anna; Martynenko, Irina; Kundelev, Evgeny; Maslov, Vladimir; Fedorov, Anatoly; Baranov, Alexander; Gun'ko, Yurii

    2016-04-01

    Here we report our investigations of the formation conditions and photophysical properties of complexes between luminescent semiconducting nanoparticles (quantum dots, QDs) and the photosensitizer chlorin e6, which is widely used for the photodynamic therapy. In our complexes, bovine serum albumin (BSA), the most abundant protein in blood serum, was used as a linker between QDs and chlorin e6 molecules. The influence of BSA on the optical properties of Ce6 and QDs in complexes was properly examined using spectral-luminescent methods. It was found that BSA passivated QD surface and substantially QD quantum yield of luminescence was increased. In addition, BSA prevented the aggregation of chlorin e6 molecules in complexes with QDs. We demonstrated that the use of BSA as a linker allows to create functional QD-chlorin e6 complexes with effective photoexcitation energy transfer from QDs to the molecules.

  17. Donor-acceptor charge transfer complexes of halogenated C{sub 60} based on ferrocene

    SciTech Connect

    Quazi, A.; Kirss, R.U.; Reiff, W.M.

    1993-12-31

    Large excess ({approximately}20/1) of the very strong reducing agent tetrakis(dimethylamino) ethylene (TDAE) has been reported to lead to N-doping of fullerene and a {open_quotes}soft{close_quotes} organic ferromagnet (T{sub c}{approximately}16K) of 1:1 stoichiometry. The authors find that fluorinated, chlorinated and brominated derivatives of C{sub 60} react rapidly in a {approximately}1:1 stoichiometry at ambient temperature with Cp{sub 2}Fe to form greenish Ch{sub 2}Ci{sub 2} solutions characteristic of Cp{sub 2}Fe{sup +}. The polycrystalline materials that precipitate have been characterized by chemical analysis and Mossbauer spectroscopy using 15 to 30% Fe-57 enriched Cp{sub 2}Fe and exhibit intense singlet spectra at ambient temperature at 77K. The isomer shifts and absence of an electric field gradient are typical of the ferricinium ion (low spin Fe{sup III}) and confirm complete charge transfer. Weak magnetic hyperfine splitting of the spectra of the ferrocene complex with C{sub 60}Cl{sub 12} suggest the possibility of three dimensional ordering for T<4.2K for this derivative. The brominated fullerene, C{sub 60}Br{sub 24} has been found to have T(eta) symmetry. The material resulting from a 1:1 stoichiometry reaction between C{sub 60}Br{sub 24} and ferrocene under an inert atmosphere spontaneously magnetically orders in zero external field with a surprisingly high critical temperature of {approximately} 14K. A rapidly relaxing phase co-exists with the ordered phase at 4.6K. This paramagnetic phase in turn undergoes 14K. A rapidly relaxing phase co-exists with the ordered phase at 4.6K. This paramagnetic phase in turn undergoes magnetic ordering upon further cooling between 4.6 and 1.32 K.

  18. Intermolecular interactions and proton transfer in the hydrogen halide-superoxide anion complexes.

    PubMed

    Lee, Sebastian J R; Mullinax, J Wayne; Schaefer, Henry F

    2016-02-17

    The superoxide radical anion O2(-) is involved in many important chemical processes spanning different scientific disciplines (e.g., environmental and biological sciences). Characterizing its interaction with various substrates to help elucidate its rich chemistry may have far reaching implications. Herein, we investigate the interaction between O2(-) (X[combining tilde] (2)Πg) and the hydrogen halides (X[combining tilde] (1)Σ) with coupled-cluster theory. In contrast to the short (1.324 Å) hydrogen bond formed between the HF and O2(-) monomers, a barrierless proton transfer occurs for the heavier hydrogen halides with the resulting complexes characterized as long (>1.89 Å) hydrogen bonds between halide anions and the HO2 radical. The dissociation energy with harmonic zero-point vibrational energy (ZPVE) for FHO2(-) (X[combining tilde] (2)A'') → HF (X[combining tilde] (1)Σ) + O2(-) (X[combining tilde] (2)Πg) is 31.2 kcal mol(-1). The other dissociation energies with ZPVE for X(-)HO2 (X[combining tilde] (2)A'') → X(-) (X[combining tilde] (1)Σ) + HO2 (X[combining tilde] (2)A'') are 25.7 kcal mol(-1) for X = Cl, 21.9 kcal mol(-1) for X = Br, and 17.9 kcal mol(-1) for X = I. Additionally, the heavier hydrogen halides can form weak halogen bonds H-XO2(-) (X[combining tilde] (2)A'') with interaction energies including ZPVE of -2.3 kcal mol(-1) for HCl, -8.3 kcal mol(-1) for HBr, and -16.7 kcal mol(-1) for HI. PMID:26852733

  19. Efficient light-harvesting using non-carbonyl carotenoids: Energy transfer dynamics in the VCP complex from Nannochloropsis oceanica.

    PubMed

    Keşan, Gürkan; Litvín, Radek; Bína, David; Durchan, Milan; Šlouf, Václav; Polívka, Tomáš

    2016-04-01

    Violaxanthin-chlorophyll a protein (VCP) from Nannochloropsis oceanica is a Chl a-only member of the LHC family of light-harvesting proteins. VCP binds carotenoids violaxanthin (Vio), vaucheriaxanthin (Vau), and vaucheriaxanthin-ester (Vau-ester). Here we report on energy transfer pathways in the VCP complex. The overall carotenoid-to-Chla energy transfer has efficiency over 90%. Based on their energy transfer properties, the carotenoids in VCP can be divided into two groups; blue carotenoids with the lowest energy absorption band around 480nm and red carotenoids with absorption extended up to 530nm. Both carotenoid groups transfer energy efficiently from their S2 states, reaching efficiencies of ~70% (blue) and ~60% (red). The S1 pathway, however, is efficient only for the red carotenoid pool for which two S1 routes characterized by 0.33 and 2.4ps time constants were identified. For the blue carotenoids the S1-mediated pathway is represented only by a minor route likely involving a hot S1 state. The relaxed S1 state of blue carotenoids decays to the ground state within 21ps. Presence of a fraction of non-transferring red carotenoids with the S1 lifetime of 13ps indicates some specific carotenoid-protein interaction that must shorten the intrinsic S1 lifetime of Vio and/or Vau whose S1 lifetimes in methanol are 26 and 29ps, respectively. The VCP complex from N. oceanica is the first example of a light-harvesting complex binding only non-carbonyl carotenoids with carotenoid-to-chlorophyll energy transfer efficiency over 90%. PMID:26744091

  20. Efficient light-harvesting using non-carbonyl carotenoids: Energy transfer dynamics in the VCP complex from Nannochloropsis oceanica.

    PubMed

    Keşan, Gürkan; Litvín, Radek; Bína, David; Durchan, Milan; Šlouf, Václav; Polívka, Tomáš

    2016-04-01

    Violaxanthin-chlorophyll a protein (VCP) from Nannochloropsis oceanica is a Chl a-only member of the LHC family of light-harvesting proteins. VCP binds carotenoids violaxanthin (Vio), vaucheriaxanthin (Vau), and vaucheriaxanthin-ester (Vau-ester). Here we report on energy transfer pathways in the VCP complex. The overall carotenoid-to-Chla energy transfer has efficiency over 90%. Based on their energy transfer properties, the carotenoids in VCP can be divided into two groups; blue carotenoids with the lowest energy absorption band around 480nm and red carotenoids with absorption extended up to 530nm. Both carotenoid groups transfer energy efficiently from their S2 states, reaching efficiencies of ~70% (blue) and ~60% (red). The S1 pathway, however, is efficient only for the red carotenoid pool for which two S1 routes characterized by 0.33 and 2.4ps time constants were identified. For the blue carotenoids the S1-mediated pathway is represented only by a minor route likely involving a hot S1 state. The relaxed S1 state of blue carotenoids decays to the ground state within 21ps. Presence of a fraction of non-transferring red carotenoids with the S1 lifetime of 13ps indicates some specific carotenoid-protein interaction that must shorten the intrinsic S1 lifetime of Vio and/or Vau whose S1 lifetimes in methanol are 26 and 29ps, respectively. The VCP complex from N. oceanica is the first example of a light-harvesting complex binding only non-carbonyl carotenoids with carotenoid-to-chlorophyll energy transfer efficiency over 90%.

  1. Energy transfer dynamics in trimers and aggregates of light-harvesting complex II probed by 2D electronic spectroscopy.

    PubMed

    Enriquez, Miriam M; Akhtar, Parveen; Zhang, Cheng; Garab, Győző; Lambrev, Petar H; Tan, Howe-Siang

    2015-06-01

    The pathways and dynamics of excitation energy transfer between the chlorophyll (Chl) domains in solubilized trimeric and aggregated light-harvesting complex II (LHCII) are examined using two-dimensional electronic spectroscopy (2DES). The LHCII trimers and aggregates exhibit the unquenched and quenched excitonic states of Chl a, respectively. 2DES allows direct correlation of excitation and emission energies of coupled states over population time delays, hence enabling mapping of the energy flow between Chls. By the excitation of the entire Chl b Qy band, energy transfer from Chl b to Chl a states is monitored in the LHCII trimers and aggregates. Global analysis of the two-dimensional (2D) spectra reveals that energy transfer from Chl b to Chl a occurs on fast and slow time scales of 240-270 fs and 2.8 ps for both forms of LHCII. 2D decay-associated spectra resulting from the global analysis identify the correlation between Chl states involved in the energy transfer and decay at a given lifetime. The contribution of singlet-singlet annihilation on the kinetics of Chl energy transfer and decay is also modelled and discussed. The results show a marked change in the energy transfer kinetics in the time range of a few picoseconds. Owing to slow energy equilibration processes, long-lived intermediate Chl a states are present in solubilized trimers, while in aggregates, the population decay of these excited states is significantly accelerated, suggesting that, overall, the energy transfer within the LHCII complexes is faster in the aggregated state.

  2. Energy transfer dynamics in trimers and aggregates of light-harvesting complex II probed by 2D electronic spectroscopy

    SciTech Connect

    Enriquez, Miriam M.; Zhang, Cheng; Tan, Howe-Siang; Akhtar, Parveen; Garab, Győző; Lambrev, Petar H.

    2015-06-07

    The pathways and dynamics of excitation energy transfer between the chlorophyll (Chl) domains in solubilized trimeric and aggregated light-harvesting complex II (LHCII) are examined using two-dimensional electronic spectroscopy (2DES). The LHCII trimers and aggregates exhibit the unquenched and quenched excitonic states of Chl a, respectively. 2DES allows direct correlation of excitation and emission energies of coupled states over population time delays, hence enabling mapping of the energy flow between Chls. By the excitation of the entire Chl b Q{sub y} band, energy transfer from Chl b to Chl a states is monitored in the LHCII trimers and aggregates. Global analysis of the two-dimensional (2D) spectra reveals that energy transfer from Chl b to Chl a occurs on fast and slow time scales of 240–270 fs and 2.8 ps for both forms of LHCII. 2D decay-associated spectra resulting from the global analysis identify the correlation between Chl states involved in the energy transfer and decay at a given lifetime. The contribution of singlet–singlet annihilation on the kinetics of Chl energy transfer and decay is also modelled and discussed. The results show a marked change in the energy transfer kinetics in the time range of a few picoseconds. Owing to slow energy equilibration processes, long-lived intermediate Chl a states are present in solubilized trimers, while in aggregates, the population decay of these excited states is significantly accelerated, suggesting that, overall, the energy transfer within the LHCII complexes is faster in the aggregated state.

  3. Allylation of acetanilides with allyl acetate under conditions of metal-complex catalysis combined with phase-transfer catalysis

    SciTech Connect

    Lebedev, S.A.; Leonova, Yu.P.; Berestova, S.S.; Petrov, E.S.

    1988-10-20

    Acetanilides are alkylated at the nitrogen atom under the conditions of phase-transfer catalysis. For the case of the reaction of acetanilides with allyl acetate the authors showed that 2-alkenyl esters can be used for the alkylation of acetanilides under the conditions of phase-transfer catalysis in the presence of the complexes of zero valent palladium. N-Acetylskatole was obtained with a yield of 50% from N-allyl-2-bromoacetanilide by intramolecular cyclization in the presence of Od(OAc)/sub 2/ as catalyst.

  4. Shifts of Gamma Phase across Primary Visual Cortical Sites Reflect Dynamic Stimulus-Modulated Information Transfer

    PubMed Central

    Besserve, Michel; Lowe, Scott C.; Logothetis, Nikos K.; Schölkopf, Bernhard; Panzeri, Stefano

    2015-01-01

    Distributed neural processing likely entails the capability of networks to reconfigure dynamically the directionality and strength of their functional connections. Yet, the neural mechanisms that may allow such dynamic routing of the information flow are not yet fully understood. We investigated the role of gamma band (50–80 Hz) oscillations in transient modulations of communication among neural populations by using measures of direction-specific causal information transfer. We found that the local phase of gamma-band rhythmic activity exerted a stimulus-modulated and spatially-asymmetric directed effect on the firing rate of spatially separated populations within the primary visual cortex. The relationships between gamma phases at different sites (phase shifts) could be described as a stimulus-modulated gamma-band wave propagating along the spatial directions with the largest information transfer. We observed transient stimulus-related changes in the spatial configuration of phases (compatible with changes in direction of gamma wave propagation) accompanied by a relative increase of the amount of information flowing along the instantaneous direction of the gamma wave. These effects were specific to the gamma-band and suggest that the time-varying relationships between gamma phases at different locations mark, and possibly causally mediate, the dynamic reconfiguration of functional connections. PMID:26394205

  5. Public Information Influences Sperm Transfer to Females in Sailfin Molly Males

    PubMed Central

    Nöbel, Sabine; Witte, Klaudia

    2013-01-01

    In animals, including humans, the social environment can serve as a public information network in which individuals can gather public information about the quality of potential mates by observing conspecifics during sexual interactions. The observing individual itself is also a part of this information network. When recognized by the observed conspecifics as an audience, his/her presence could influence the sexual interaction between those individuals, because the observer might be considered as a potential mate or competitor. One of the most challenging questions in sexual selection to date is how the use of public information in the context of mate choice is linked to the fitness of individuals. Here, we could show that public information influences mate-choice behaviour in sailfin molly males, Poecilia latipinna, and influences the amount of sperm males transfer to a female partner. In the presence of an audience male, males spent less time with the previously preferred, larger of two females and significantly more time with the previously non-preferred, smaller female. When males could physically interact with a female and were faced with an audience male, three audience females or no audience, males transferred significantly more sperm to a female partner in the presence of an audience male than with female audience or no audience and spent less time courting his female partner. This is the first study showing that public information use turns into fitness investment, which is the crucial factor to understand the role of public information in the dynamic processes in sexual selection. PMID:23342021

  6. Analysing the information flow between financial time series . An improved estimator for transfer entropy

    NASA Astrophysics Data System (ADS)

    Marschinski, R.; Kantz, H.

    2002-11-01

    Following the recently introduced concept of transfer entropy, we attempt to measure the information flow between two financial time series, the Dow Jones and DAX stock index. Being based on Shannon entropies, this model-free approach in principle allows us to detect statistical dependencies of all types, i.e. linear and nonlinear temporal correlations. However, when available data is limited and the expected effect is rather small, a straightforward implementation suffers badly from misestimation due to finite sample effects, making it basically impossible to assess the significance of the obtained values. We therefore introduce a modified estimator, called effective transfer entropy, which leads to improved results in such conditions. In the application, we then manage to confirm an information transfer on a time scale of one minute between the two financial time series. The different economic impact of the two indices is also recovered from the data. Numerical results are then interpreted on one hand as capability of one index to explain future observations of the other, and on the other hand within terms of coupling strengths in the framework of a bivariate autoregressive stochastic model. Evidence is given for a nonlinear character of the coupling between Dow Jones and DAX.

  7. Phenylketonuria and Complex Spatial Visualization: An Analysis of Information Processing.

    ERIC Educational Resources Information Center

    Brunner, Robert L.; And Others

    1987-01-01

    The study of the ability of 16 early treated phenylketonuric (PKU) patients (ages 6-23 years) to solve complex spatial problems suggested that choice of problem-solving strategy, attention span, and accuracy of mental representation may be affected in PKU patients, despite efforts to maintain well-controlled phenylalanine concentrations in the…

  8. Dynamics of information diffusion and its applications on complex networks

    NASA Astrophysics Data System (ADS)

    Zhang, Zi-Ke; Liu, Chuang; Zhan, Xiu-Xiu; Lu, Xin; Zhang, Chu-Xu; Zhang, Yi-Cheng

    2016-09-01

    The ongoing rapid expansion of the Word Wide Web (WWW) greatly increases the information of effective transmission from heterogeneous individuals to various systems. Extensive research for information diffusion is introduced by a broad range of communities including social and computer scientists, physicists, and interdisciplinary researchers. Despite substantial theoretical and empirical studies, unification and comparison of different theories and approaches are lacking, which impedes further advances. In this article, we review recent developments in information diffusion and discuss the major challenges. We compare and evaluate available models and algorithms to respectively investigate their physical roles and optimization designs. Potential impacts and future directions are discussed. We emphasize that information diffusion has great scientific depth and combines diverse research fields which makes it interesting for physicists as well as interdisciplinary researchers.

  9. Scale effects on information content and complexity of streamflows

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Understanding temporal and spatial variations of streamflows is important for flood forecasting, water resources management, and revealing interactions between hydrologic processes (e.g., precipitation, evapotranspiration, and soil water and groundwater flows.) The information theory has been used i...

  10. Statistical complexity in the hydrological information from urbanizing basins

    NASA Astrophysics Data System (ADS)

    Jovanovic, T.; Mejia, A.; Siddique, R.; Gironas, J. A.

    2014-12-01

    Urbanizing basins (i.e. basins under urban growth) typify coupled human-natural (CHN) systems, which are said to be complex. Furthermore, the level of complexity of these basins could be assumed to depend on how much the natural environment has been disturbed. In this study we attempt to characterize these systems by quantifying their statistical complexity and its linkage with the degree of urbanization. To perform this quantification, we use both multifractal detrended fluctuation analysis (MDFA) and permutation entropy (PE). MDFA is used to determine long-term dependencies, the Hurst exponent, and the level of multifractality in the hydrological records. On the other hand, PE is used to characterize short-term dependencies and determine the degree of statistical complexity in the records using a metric that depends non-trivially on entropy. The MDFA and PE analysis were applied to long-term hydrologic records (streamflow, baseflow, and rainfall) from 20 urbanizing basins located in the metropolitan areas of Baltimore, Philadelphia, and Washington DC, US. Results show that streamflow in urbanizing basins displays scaling over a wide range of temporal scales, as well as multifractal properties. More relevantly, we found that the scaling and the strength of the multifractality tend to weaken as the basins become more urbanized (i.e. streamflow records become more similar to the driving rainfall forcing with increasing urbanization). This interpretation is supported by the non-significant dependency of baseflow on the amount of urban development in the basin. The PE analysis shows that the statistical complexity of streamflow decreases for the most urbanized basins while the entropy increases, thereby suggesting that streamflow become less structured and more random with increasing urbanization. Overall, this study illustrates the potential of the analysis performed and associated metrics to characterize the hydrological impact of urbanization.

  11. ELAS - A geobased information system that is transferable to several computers. [Earth resources Laboratory Applications Software

    NASA Technical Reports Server (NTRS)

    Whitley, S. L.; Pearson, R. W.; Seyfarth, B. R.; Graham, M. H.

    1981-01-01

    In the early years of remote sensing, emphasis was placed on the processing and analysis of data from a single multispectral sensor, such as the Landsat Multispectral Scanner System (MSS). However, in connection with attempts to use the data for resource management, it was realized that many deficiencies existed in single data sets. A need was established to geographically reference the MSS data and to register with it data from disparate sources. Technological transfer activities have required systems concepts that can be easily transferred to computers of different types in other organizations. ELAS (Earth Resources Laboratory Applications Software), a geographically based information system, was developed to meet the considered needs. ELAS accepts data from a variety of sources. It contains programs to geographically reference the data to the Universal Transverse Mercator grid. One of the primary functions of ELAS is to produce a surface cover map.

  12. Genes, information and sense: complexity and knowledge retrieval.

    PubMed

    Sadovsky, Michael G; Putintseva, Julia A; Shchepanovsky, Alexander S

    2008-06-01

    Information capacity of nucleotide sequences measures the unexpectedness of a continuation of a given string of nucleotides, thus having a sound relation to a variety of biological issues. A continuation is defined in a way maximizing the entropy of the ensemble of such continuations. The capacity is defined as a mutual entropy of real frequency dictionary of a sequence with respect to the one bearing the most expected continuations; it does not depend on the length of strings contained in a dictionary. Various genomes exhibit a multi-minima pattern of the dependence of information capacity on the string length, thus reflecting an order within a sequence. The strings with significant deviation of an expected frequency from the real one are the words of increased information value. Such words exhibit a non-random distribution alongside a sequence, thus making it possible to retrieve the correlation between a structure, and a function encoded within a sequence.

  13. Genes, information and sense: complexity and knowledge retrieval.

    PubMed

    Sadovsky, Michael G; Putintseva, Julia A; Shchepanovsky, Alexander S

    2008-06-01

    Information capacity of nucleotide sequences measures the unexpectedness of a continuation of a given string of nucleotides, thus having a sound relation to a variety of biological issues. A continuation is defined in a way maximizing the entropy of the ensemble of such continuations. The capacity is defined as a mutual entropy of real frequency dictionary of a sequence with respect to the one bearing the most expected continuations; it does not depend on the length of strings contained in a dictionary. Various genomes exhibit a multi-minima pattern of the dependence of information capacity on the string length, thus reflecting an order within a sequence. The strings with significant deviation of an expected frequency from the real one are the words of increased information value. Such words exhibit a non-random distribution alongside a sequence, thus making it possible to retrieve the correlation between a structure, and a function encoded within a sequence. PMID:18443840

  14. Snapshot blotting: transfer of nucleic acids and nucleoprotein complexes from electrophoresis gels to grids for electron microscopy.

    PubMed Central

    Jett, S D; Bear, D G

    1994-01-01

    We present a technique, "snapshot blotting," for the electrophoretic transfer of nucleic acids and nucleoprotein complexes in gel electrophoresis bands onto highly stable carbon film-coated grids for imaging by electron microscopy. The method permits structural analysis of macromolecular species that have been resolved by a gel mobility-shift assay. To demonstrate the efficiency and integrity of the transfer process for a multiprotein-DNA assembly, we have imaged various species of a prokaryotic transcription complex, using the cleavage-defective EcoRI(Q111) protein as an orientation marker and as a blockade of transcription elongation. Snapshot blotting should be of great utility in the structural characterization of nucleic acids and protein-nucleic acid interactions. Images PMID:8041711

  15. Making sense in a complex landscape: how the Cynefin Framework from Complex Adaptive Systems Theory can inform health promotion practice.

    PubMed

    Van Beurden, Eric K; Kia, Annie M; Zask, Avigdor; Dietrich, Uta; Rose, Lauren

    2013-03-01

    Health promotion addresses issues from the simple (with well-known cause/effect links) to the highly complex (webs and loops of cause/effect with unpredictable, emergent properties). Yet there is no conceptual framework within its theory base to help identify approaches appropriate to the level of complexity. The default approach favours reductionism--the assumption that reducing a system to its parts will inform whole system behaviour. Such an approach can yield useful knowledge, yet is inadequate where issues have multiple interacting causes, such as social determinants of health. To address complex issues, there is a need for a conceptual framework that helps choose action that is appropriate to context. This paper presents the Cynefin Framework, informed by complexity science--the study of Complex Adaptive Systems (CAS). It introduces key CAS concepts and reviews the emergence and implications of 'complex' approaches within health promotion. It explains the framework and its use with examples from contemporary practice, and sets it within the context of related bodies of health promotion theory. The Cynefin Framework, especially when used as a sense-making tool, can help practitioners understand the complexity of issues, identify appropriate strategies and avoid the pitfalls of applying reductionist approaches to complex situations. The urgency to address critical issues such as climate change and the social determinants of health calls for us to engage with complexity science. The Cynefin Framework helps practitioners make the shift, and enables those already engaged in complex approaches to communicate the value and meaning of their work in a system that privileges reductionist approaches. PMID:22128193

  16. Making sense in a complex landscape: how the Cynefin Framework from Complex Adaptive Systems Theory can inform health promotion practice.

    PubMed

    Van Beurden, Eric K; Kia, Annie M; Zask, Avigdor; Dietrich, Uta; Rose, Lauren

    2013-03-01

    Health promotion addresses issues from the simple (with well-known cause/effect links) to the highly complex (webs and loops of cause/effect with unpredictable, emergent properties). Yet there is no conceptual framework within its theory base to help identify approaches appropriate to the level of complexity. The default approach favours reductionism--the assumption that reducing a system to its parts will inform whole system behaviour. Such an approach can yield useful knowledge, yet is inadequate where issues have multiple interacting causes, such as social determinants of health. To address complex issues, there is a need for a conceptual framework that helps choose action that is appropriate to context. This paper presents the Cynefin Framework, informed by complexity science--the study of Complex Adaptive Systems (CAS). It introduces key CAS concepts and reviews the emergence and implications of 'complex' approaches within health promotion. It explains the framework and its use with examples from contemporary practice, and sets it within the context of related bodies of health promotion theory. The Cynefin Framework, especially when used as a sense-making tool, can help practitioners understand the complexity of issues, identify appropriate strategies and avoid the pitfalls of applying reductionist approaches to complex situations. The urgency to address critical issues such as climate change and the social determinants of health calls for us to engage with complexity science. The Cynefin Framework helps practitioners make the shift, and enables those already engaged in complex approaches to communicate the value and meaning of their work in a system that privileges reductionist approaches.

  17. Optical studies of the charge transfer complex in polythiophene/fullerene blends for organic photovoltaic applications

    NASA Astrophysics Data System (ADS)

    Drori, T.; Holt, J.; Vardeny, Z. V.

    2010-08-01

    We studied the photophysics of regioregular polythiophene/ C61 (RR-P3HT/PCBM) blend films utilized for organic photovoltaic applications using the femtosecond transient and steady-state photomodulation techniques with above-gap and below-gap pump excitations and electroabsorption spectroscopy. We provide strong evidence for the existence of charge transfer complex (CTC) state in the blend that is formed deep inside the optical gap of the polymer and fullerene constituents, which is clearly revealed in the electroabsorption spectrum with an onset at 1.2 eV. We identify this “midgap” band as the lowest lying CTC state formed at the interfaces separating the polymer and fullerene phases. With above-gap pump excitation the primary photoexcitations in the blend are excitons and polarons in the polymer domains that are generated within the experimental time resolution (150 fs), having distinguishable photoinduced absorption (PA) bands in the mid-IR. The photogenerated excitons subsequently decay within ˜10ps , consistent with the polymer weak photoluminescence in the blend. In contrast, with below-gap pump excitation, a new PA band in the mid-IR is generated within our time resolution, which is associated with photogenerated species that decay into polarons at much later times; also no PA of excitons is observed. We interpret the photoexcitations as CT excitons, which with below-gap pump excitation are resonantly generated on the CTC states at the interfaces, as the first step for polaron generation, without involving intrachain excitons in the polymer phase. We found that the polarons generated with below-gap pump excitation are trapped at the interfaces with relatively long lifetime, and thus may generate polarons on the polymer chains and fullerene molecules with a different mechanism than with above-gap excitation. In any case the interfacial polarons generated with below-gap excitation do not substantially contribute to the photocurrent density in photovoltaic

  18. Osmium pyme complexes for fast hydrogenation and asymmetric transfer hydrogenation of ketones.

    PubMed

    Baratta, Walter; Ballico, Maurizio; Del Zotto, Alessandro; Siega, Katia; Magnolia, Santo; Rigo, Pierluigi

    2008-01-01

    The osmium compound trans,cis-[OsCl2(PPh3)2(Pyme)] (1) (Pyme=1-(pyridin-2-yl)methanamine), obtained from [OsCl2(PPh3)3] and Pyme, thermally isomerizes to cis,cis-[OsCl2(PPh3)(2)(Pyme)] (2) in mesitylene at 150 degrees C. Reaction of [OsCl2(PPh3)3] with Ph2P(CH2)(4)PPh2 (dppb) and Pyme in mesitylene (150 degrees C, 4 h) leads to a mixture of trans-[OsCl2(dppb)(Pyme)] (3) and cis-[OsCl2(dppb)(Pyme)] (4) in about an 1:3 molar ratio. The complex trans-[OsCl2(dppb)(Pyet)] (5) (Pyet=2-(pyridin-2-yl)ethanamine) is formed by reaction of [OsCl2(PPh3)3] with dppb and Pyet in toluene at reflux. Compounds 1, 2, 5 and the mixture of isomers 3/4 efficiently catalyze the transfer hydrogenation (TH) of different ketones in refluxing 2-propanol and in the presence of NaOiPr (2.0 mol %). Interestingly, 3/4 has been proven to reduce different ketones (even bulky) by means of TH with a remarkably high turnover frequency (TOF up to 5.7 x 10(5) h(-1)) and at very low loading (0.05-0.001 mol %). The system 3/4 also efficiently catalyzes the hydrogenation of many ketones (H2, 5.0 atm) in ethanol with KOtBu (2.0 mol %) at 70 degrees C (TOF up to 1.5 x 10(4) h(-1)). The in-situ-generated catalysts prepared by the reaction of [OsCl2(PPh3)3] with Josiphos diphosphanes and (+/-)-1-alkyl-substituted Pyme ligands, promote the enantioselective TH of different ketones with 91-96 % ee (ee=enantiomeric excess) and with a TOF of up to 1.9 x 10(4) h(-1) at 60 degrees C.

  19. Switchover of the Mechanism between Electron Transfer and Hydrogen-Atom Transfer for a Protonated Manganese(IV)-Oxo Complex by Changing Only the Reaction Temperature.

    PubMed

    Jung, Jieun; Kim, Surin; Lee, Yong-Min; Nam, Wonwoo; Fukuzumi, Shunichi

    2016-06-20

    Hydroxylation of mesitylene by a nonheme manganese(IV)-oxo complex, [(N4Py)Mn(IV) (O)](2+) (1), proceeds via one-step hydrogen-atom transfer (HAT) with a large deuterium kinetic isotope effect (KIE) of 3.2(3) at 293 K. In contrast, the same reaction with a triflic acid-bound manganese(IV)-oxo complex, [(N4Py)Mn(IV) (O)](2+) -(HOTf)2 (2), proceeds via electron transfer (ET) with no KIE at 293 K. Interestingly, when the reaction temperature is lowered to less than 263 K in the reaction of 2, however, the mechanism changes again from ET to HAT with a large KIE of 2.9(3). Such a switchover of the reaction mechanism from ET to HAT is shown to occur by changing only temperature in the boundary region between ET and HAT pathways when the driving force of ET from toluene derivatives to 2 is around -0.5 eV. The present results provide a valuable and general guide to predict a switchover of the reaction mechanism from ET to the others, including HAT. PMID:27191357

  20. Molecular dynamics simulations give insight into the conformational change, complex formation, and electron transfer pathway for cytochrome P450 reductase

    PubMed Central

    Sündermann, Axel; Oostenbrink, Chris

    2013-01-01

    Cytochrome P450 reductase (CYPOR) undergoes a large conformational change to allow for an electron transfer to a redox partner to take place. After an internal electron transfer over its cofactors, it opens up to facilitate the interaction and electron transfer with a cytochrome P450. The open conformation appears difficult to crystallize. Therefore, a model of a human CYPOR in the open conformation was constructed to be able to investigate the stability and conformational change of this protein by means of molecular dynamics simulations. Since the role of the protein is to provide electrons to a redox partner, the interactions with cytochrome P450 2D6 (2D6) were investigated and a possible complex structure is suggested. Additionally, electron pathway calculations with a newly written program were performed to investigate which amino acids relay the electrons from the FMN cofactor of CYPOR to the HEME of 2D6. Several possible interacting amino acids in the complex, as well as a possible electron transfer pathway were identified and open the way for further investigation by site directed mutagenesis studies. PMID:23832577