WorldWideScience

Sample records for dynamics transcending chemical

  1. Cluster dynamics transcending chemical dynamics toward nuclear fusion.

    Science.gov (United States)

    Heidenreich, Andreas; Jortner, Joshua; Last, Isidore

    2006-07-11

    Ultrafast cluster dynamics encompasses femtosecond nuclear dynamics, attosecond electron dynamics, and electron-nuclear dynamics in ultraintense laser fields (peak intensities 10(15)-10(20) W.cm(-2)). Extreme cluster multielectron ionization produces highly charged cluster ions, e.g., (C(4+)(D(+))(4))(n) and (D(+)I(22+))(n) at I(M) = 10(18) W.cm(-2), that undergo Coulomb explosion (CE) with the production of high-energy (5 keV to 1 MeV) ions, which can trigger nuclear reactions in an assembly of exploding clusters. The laser intensity and the cluster size dependence of the dynamics and energetics of CE of (D(2))(n), (HT)(n), (CD(4))(n), (DI)(n), (CD(3)I)(n), and (CH(3)I)(n) clusters were explored by electrostatic models and molecular dynamics simulations, quantifying energetic driving effects, and kinematic run-over effects. The optimization of table-top dd nuclear fusion driven by CE of deuterium containing heteroclusters is realized for light-heavy heteroclusters of the largest size, which allows for the prevalence of cluster vertical ionization at the highest intensity of the laser field. We demonstrate a 7-orders-of-magnitude enhancement of the yield of dd nuclear fusion driven by CE of light-heavy heteroclusters as compared with (D(2))(n) clusters of the same size. Prospective applications for the attainment of table-top nucleosynthesis reactions, e.g., (12)C(P,gamma)(13)N driven by CE of (CH(3)I)(n) clusters, were explored.

  2. Operational dynamic modeling transcending quantum and classical mechanics.

    Science.gov (United States)

    Bondar, Denys I; Cabrera, Renan; Lompay, Robert R; Ivanov, Misha Yu; Rabitz, Herschel A

    2012-11-09

    We introduce a general and systematic theoretical framework for operational dynamic modeling (ODM) by combining a kinematic description of a model with the evolution of the dynamical average values. The kinematics includes the algebra of the observables and their defined averages. The evolution of the average values is drawn in the form of Ehrenfest-like theorems. We show that ODM is capable of encompassing wide-ranging dynamics from classical non-relativistic mechanics to quantum field theory. The generality of ODM should provide a basis for formulating novel theories.

  3. Exploring transcendence in EFL learners’ reading comprehension through computerized dynamic assessment

    Directory of Open Access Journals (Sweden)

    Saman Ebadi

    2016-01-01

    Full Text Available Derived from Vygotsky’s works, dynamic assessment (DA enables learners to move beyond their current level of functioning through offering needs-sensitized mediation. This study aimed at exploring the learners’ development in novel and increasingly more challenging situations called transcendence (TR in an L2 context focusing on reading comprehension through computerized dynamic assessment (CDA. An overall number of 32 BA TEFL advanced students were selected from among undergraduates of a university in Iran to participate in this study. To fulfil the purpose of the study, the researchers developed Computerized Dynamic Reading Assessment to examine Transcendence (CDRAT software which included reading comprehension CDA tests. To monitor the maintenance of learning in different time intervals, two software programs named CDRAT1 and CDRAT2 were utilized in specific time intervals after the posttest. The results indicated that not only did increased task complexity not lead to regression of students’ development, but also it had an effect on enhancing their development. Thus, transcendence had an effect on the generalizability of the contentions to a great extent. In conclusion, it was disclosed that there is no endpoint to progress and merely gaining a low or high score should not be interpreted as the inability of a special learner to surpass. This would more reinforce the need for applying TR in other future DA studies.

  4. Transcendence and Sensoriness

    DEFF Research Database (Denmark)

    Protestant theology and culture are known for a reserved, at times skeptical, attitude to the use of art and aesthetic forms of expression in a religious context. In Transcendence and Sensoriness, this attitude is analysed and discussed both theoretically and through case studies considered...

  5. Probing Chemical Dynamics at Surfaces

    Institute of Scientific and Technical Information of China (English)

    KLEYN, A.W.; KLEYN, A.W

    2001-01-01

    An account is given of recent progress concerning chemical reaction dynamics at surfaces. The goal is to elucidate the reaction dynamics at the molecular level, both as time and distance is concerned. The methods of study include molecular beam scattering, scanning tunnelling microscopy, and (femtosecond) laser spectroscopy. Systems studied include elementary interactions of NO, CO, and O2 at single crystal metal surfaces.

  6. Transcending the nation state

    DEFF Research Database (Denmark)

    Cort, Pia

    2009-01-01

    Throughout Europe, vocational education and training is undergoing reform and modernisation as part of a common EU policy process, the Copenhagen Process. The aim of this Process is initiate a pan-European modernisation of vocational education and training in order to meet the challenges of global...... is under construction which aims to transcend the nation state by introducing a new way of "thinking" vocational education and training....

  7. Kinematically complete chemical reaction dynamics

    Science.gov (United States)

    Trippel, S.; Stei, M.; Otto, R.; Hlavenka, P.; Mikosch, J.; Eichhorn, C.; Lourderaj, U.; Zhang, J. X.; Hase, W. L.; Weidemüller, M.; Wester, R.

    2009-11-01

    Kinematically complete studies of molecular reactions offer an unprecedented level of insight into the dynamics and the different mechanisms by which chemical reactions occur. We have developed a scheme to study ion-molecule reactions by velocity map imaging at very low collision energies. Results for the elementary nucleophilic substitution (SN2) reaction Cl- + CH3I → ClCH3 + I- are presented and compared to high-level direct dynamics trajectory calculations. Furthermore, an improved design of the crossed-beam imaging spectrometer with full three-dimensional measurement capabilities is discussed and characterization measurements using photoionization of NH3 and photodissociation of CH3I are presented.

  8. Nonlinear Chemical Dynamics and Synchronization

    Science.gov (United States)

    Li, Ning

    Alan Turing's work on morphogenesis, more than half a century ago, continues to motivate and inspire theoretical and experimental biologists even today. That said, there are very few experimental systems for which Turing's theory is applicable. In this thesis we present an experimental reaction-diffusion system ideally suited for testing Turing's ideas in synthetic "cells" consisting of microfluidically produced surfactant-stabilized emulsions in which droplets containing the Belousov-Zhabotinsky (BZ) oscillatory chemical reactants are dispersed in oil. The BZ reaction has become the prototype of nonlinear dynamics in chemistry and a preferred system for exploring the behavior of coupled nonlinear oscillators. Our system consists of a surfactant stabilized monodisperse emulsion of drops of aqueous BZ solution dispersed in a continuous phase of oil. In contrast to biology, here the chemistry is understood, rate constants are measured and interdrop coupling is purely diffusive. We explore a large set of parameters through control of rate constants, drop size, spacing, and spatial arrangement of the drops in lines and rings in one-dimension (1D) and hexagonal arrays in two-dimensions (2D). The Turing model is regarded as a metaphor for morphogenesis in biology but not for prediction. Here, we develop a quantitative and falsifiable reaction-diffusion model that we experimentally test with synthetic cells. We quantitatively establish the extent to which the Turing model in 1D describes both stationary pattern formation and temporal synchronization of chemical oscillators via reaction-diffusion and in 2D demonstrate that chemical morphogenesis drives physical differentiation in synthetic cells.

  9. Transcendence of Certain Trigonometric Series

    Institute of Scientific and Technical Information of China (English)

    Yao Chen ZHU

    2002-01-01

    In this paper the transcendence of values of certain trigonometric series with algebraiccoefficients and its derivatives at algebraic points is proved under a genera] condition dependent onlyon the coefficients. The proof of the theorem is based on a criterion for linear independence over anumber field.

  10. Gas-phase chemical dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Weston, R.E. Jr.; Sears, T.J.; Preses, J.M. [Brookhaven National Laboratory, Upton, NY (United States)

    1993-12-01

    Research in this program is directed towards the spectroscopy of small free radicals and reactive molecules and the state-to-state dynamics of gas phase collision, energy transfer, and photodissociation phenomena. Work on several systems is summarized here.

  11. Chemical kinetics and reaction dynamics

    CERN Document Server

    Houston, Paul L

    2006-01-01

    This text teaches the principles underlying modern chemical kinetics in a clear, direct fashion, using several examples to enhance basic understanding. It features solutions to selected problems, with separate sections and appendices that cover more technical applications.Each chapter is self-contained and features an introduction that identifies its basic goals, their significance, and a general plan for their achievement. This text's important aims are to demonstrate that the basic kinetic principles are essential to the solution of modern chemical problems, and to show how the underlying qu

  12. Chemical Dynamics at the Advanced Light Source

    Energy Technology Data Exchange (ETDEWEB)

    Baer, T.; Berrah, N.; Fadley, C.; Moore, C.B.; Neumark, D.M.; Ng, C.Y.; Ruscic, B.; Smith, N.V.; Suits, A.G.; Wodtke, A.M.

    1999-02-02

    A day-long retreat was held January 15, 1999 to chart the future directions for chemical dynamics studies at the Advanced Light Source. This represents an important period for the Chemical Dynamics Beamline, as the hardware is well-developed, most of the initial experimental objectives have been realized and the mission is now to identify the future scientific priorities for the beamline and attract users of the highest caliber. To this end, we have developed a detailed scientific program for the near term; identified and prioritized the long range scientific opportunities, identified essential new hardware, and outlined an aggressive outreach program to involve the chemical physics community.

  13. Chemical structure and dynamics. Annual report 1995

    Energy Technology Data Exchange (ETDEWEB)

    Colson, S.D.; McDowell, R.S.

    1996-05-01

    The Chemical Structure and Dynamics program is a major component of Pacific Northwest National Laboratory`s Environmental Molecular Sciences Laboratory (EMSL), providing a state-of-the-art collaborative facility for studies of chemical structure and dynamics. We respond to the need for a fundamental, molecular-level understanding of chemistry at a wide variety of environmentally important interfaces by (1) extending the experimental characterization and theoretical description of chemical reactions to encompass the effects of condensed media and interfaces; (2) developing a multidisciplinary capability for describing interfacial chemical processes within which the new knowledge generated can be brought to bear on complex phenomena in environmental chemistry and in nuclear waste processing and storage; and (3) developing state-of-the-art analytical methods for the characterization of waste tanks and pollutant distributions, and for detection and monitoring of trace atmospheric species.

  14. Chemical structure and dynamics: Annual report 1996

    Energy Technology Data Exchange (ETDEWEB)

    Colson, S.D.; McDowell, R.S.

    1997-03-01

    The Chemical Structure and Dynamics (CS&D) program is a major component of the William R. Wiley Environmental Molecular Sciences Laboratory (EMSL) developed by Pacific Northwest National Laboratory (PNNL) to provide a state-of-the-art collaborative facility for studies of chemical structure and dynamics. We respond to the need for a fundamental, molecular-level understanding of chemistry at a wide variety of environmentally important interfaces by (1) extending the experimental characterization and theoretical description of chemical reactions to encompass the effects of condensed media and interfaces; (2) developing a multidisciplinary capability for describing interfacial chemical processes within which the new knowledge generated can be brought to bear on complex phenomena in environmental chemistry and in nuclear waste processing and storage; and (3) developing state-of-the-art analytical methods for characterizing waste tanks and pollutant distributions, and for detecting and monitoring trace atmospheric species.

  15. Annual Report 2000. Chemical Structure and Dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Colson, Steven D.; McDowell, Robin S.

    2001-04-15

    This annual report describes the research and accomplishments of the Chemical Structure and Dynamics Program in the year 2000, one of six research programs at the William R. Wiley Environmental Molecular Sciences Laboratory (EMSL) - a multidisciplinary, national scientific user facility and research organization. The Chemical Structure and Dynamics (CS&D) program is meeting the need for a fundamental, molecular-level understanding by 1) extending the experimental characterization and theoretical description of chemical reactions to encompass the effects of condensed media and interfaces; 2) developing a multidisciplinary capability for describing interfacial chemical processes relevant to environmental chemistry; and 3) developing state-of-the-art research and analytical methods for characterizing complex materials of the types found in natural and contaminated systems.

  16. Chemical structure and dynamics: Annual report 1993

    Energy Technology Data Exchange (ETDEWEB)

    Colson, S.D.

    1994-07-01

    The Chemical Structure and Dynamics program responds to the need for a fundamental, molecular-level understanding of chemistry at the wide variety of environmentally-important interfaces. The research program is built around the established relationship between structure, thermodynamics, and kinetics. This research effort continues to evolve into a program of rigorous studies of fundamental molecular processes in model systems (e.g., well-characterized surfaces, single-component solutions, clusters, and biological molecules), and studies of complex systems found in the environment. Experimental studies of molecular and supramolecular structures and thermodynamics are key to understanding the nature of matter, and lead to direct comparison with computational results. Kinetic and mechanistic measurements, combined with real-time dynamics measurements of atomic and molecular motions during chemical reactions, provide for a molecular-level description of chemical reactions. The anticipated results of this work are the achievement of a quantitative understanding of chemical processes at complex interfaces, the development of new techniques for the detection and measurement of species at such interfaces, and the interpretation and extrapolation of the observations in terms of models of interfacial chemistry. The Chemical Structure and Dynamics research program includes five areas described in detail in this report: Reaction mechanisms at solid interfaces; Solution and solution interfaces; Structure and dynamics of biological systems; Analytical methods development; and atmospheric chemistry. Extended abstracts are presented for 23 studies.

  17. Chemical Reaction Dynamics in Nanoscle Environments

    Energy Technology Data Exchange (ETDEWEB)

    Evelyn M. Goldfield

    2006-09-26

    The major focus of the research in this program is the study of the behavior of molecular systems confined in nanoscale environments. The goal is to develop a theoretical framework for predicting how chemical reactions occur in nanoscale environments. To achieve this goal we have employed ab initio quantum chemistry, classical dynamics and quantum dynamics methods. Much of the research has focused on the behavior of molecules confined within single-walled carbon nanotubes (SWCNTs). We have also studied interactions of small molecules with the exterior surface of SWCNTs. Nonequilibrium molecular dynamics of interfaces of sliding surface interfaces have also been performed.

  18. DNA-Encoded Dynamic Combinatorial Chemical Libraries.

    Science.gov (United States)

    Reddavide, Francesco V; Lin, Weilin; Lehnert, Sarah; Zhang, Yixin

    2015-06-26

    Dynamic combinatorial chemistry (DCC) explores the thermodynamic equilibrium of reversible reactions. Its application in the discovery of protein binders is largely limited by difficulties in the analysis of complex reaction mixtures. DNA-encoded chemical library (DECL) technology allows the selection of binders from a mixture of up to billions of different compounds; however, experimental results often show low a signal-to-noise ratio and poor correlation between enrichment factor and binding affinity. Herein we describe the design and application of DNA-encoded dynamic combinatorial chemical libraries (EDCCLs). Our experiments have shown that the EDCCL approach can be used not only to convert monovalent binders into high-affinity bivalent binders, but also to cause remarkably enhanced enrichment of potent bivalent binders by driving their in situ synthesis. We also demonstrate the application of EDCCLs in DNA-templated chemical reactions.

  19. Transcending Organization in Temporary Systems

    DEFF Research Database (Denmark)

    Stjerne, Iben Sandal

    in temporary systems that lack stability and formal order. It advances our understanding of transcending organization in creative industries by adopting a practice based perspective. Empirically, the dissertation presents an in-depth study of the Danish film industry, which is an extreme case of a project...... based industry wherein temporary organizing dominates and challenges people to organize employment and work in new ways. The study draws on both ethnographic work and interviews conducted in the period from 2009-2015. The data set consist of 40 in-depth interviews of career trajectories with successful......Because of their temporary nature, work and employment in project based organizations are different from what we used to see in traditional organizational forms. Temporary employment, entailing less stability within the organization changes how employment and work are organized. Temporary systems...

  20. Transcended power of the state

    DEFF Research Database (Denmark)

    Arnholtz, Jens; Hammerslev, Ole

    2013-01-01

    Pierre Bourdieu's writings on the state consist of a series of more or less coherent investigations approaching the state from different angles. His writings on the state may seem to contain internal ambiguities. On the one hand, they argue for an actor-centered approach to the state while......, on the other hand, elaborating the power of the state as an institution transcending these actors. The purpose of this article is to reconstruct Bourdieu's understanding of the state in order to examine if the opposition between these two apparently opposite approaches are in as sharp contention as they first...... appear. The article starts out by discussing how Bourdieu has approached the state through his broader sociological approach and concepts. Afterwards it outlines the state formation processes lying at the foundation of the state's power. Next it focuses on his special emphasis on the actor strategies...

  1. Transcending Organization in Temporary Systems

    DEFF Research Database (Denmark)

    Stjerne, Iben Sandal

    in temporary systems that lack stability and formal order. It advances our understanding of transcending organization in creative industries by adopting a practice based perspective. Empirically, the dissertation presents an in-depth study of the Danish film industry, which is an extreme case of a project...... based industry wherein temporary organizing dominates and challenges people to organize employment and work in new ways. The study draws on both ethnographic work and interviews conducted in the period from 2009-2015. The data set consist of 40 in-depth interviews of career trajectories with successful......Because of their temporary nature, work and employment in project based organizations are different from what we used to see in traditional organizational forms. Temporary employment, entailing less stability within the organization changes how employment and work are organized. Temporary systems...

  2. Nanomotor dynamics in a chemically oscillating medium

    Science.gov (United States)

    Robertson, Bryan; Kapral, Raymond

    2015-04-01

    Synthetic nanomotors powered by chemical reactions have potential uses as cargo transport vehicles in both in vivo and in vitro applications. In many situations, motors will have to operate in out-of-equilibrium complex chemically reacting media, which supply fuel to the motors and remove the products they produce. Using molecular simulation and mean-field theory, this paper describes some of the new features that arise when a chemically powered nanomotor, operating through a diffusiophoretic mechanism, moves in an environment that supports an oscillatory chemical reaction network. It is shown how oscillations in the concentrations in chemical species in the environment give rise to oscillatory motor dynamics. More importantly, since the catalytic reactions on the motor that are responsible for its propulsion couple to the bulk phase reaction network, the motor can change its local environment. This process can give rise to distinctive spatiotemporal structures in reaction-diffusion media that occur as a result of active motor motion. Such locally induced nonequilibrium structure will play an important role in applications that involve motor dynamics in complex chemical media.

  3. Nanomotor dynamics in a chemically oscillating medium

    Energy Technology Data Exchange (ETDEWEB)

    Robertson, Bryan, E-mail: bryan.robertson@mail.utoronto.ca; Kapral, Raymond, E-mail: rkapral@chem.utoronto.ca [Chemical Physics Theory Group, Department of Chemistry, University of Toronto, Toronto, Ontario M5S 3H6 (Canada)

    2015-04-21

    Synthetic nanomotors powered by chemical reactions have potential uses as cargo transport vehicles in both in vivo and in vitro applications. In many situations, motors will have to operate in out-of-equilibrium complex chemically reacting media, which supply fuel to the motors and remove the products they produce. Using molecular simulation and mean-field theory, this paper describes some of the new features that arise when a chemically powered nanomotor, operating through a diffusiophoretic mechanism, moves in an environment that supports an oscillatory chemical reaction network. It is shown how oscillations in the concentrations in chemical species in the environment give rise to oscillatory motor dynamics. More importantly, since the catalytic reactions on the motor that are responsible for its propulsion couple to the bulk phase reaction network, the motor can change its local environment. This process can give rise to distinctive spatiotemporal structures in reaction-diffusion media that occur as a result of active motor motion. Such locally induced nonequilibrium structure will play an important role in applications that involve motor dynamics in complex chemical media.

  4. Transcendence and Transcending in the Theology of Father Dumitru Stăniloae

    Directory of Open Access Journals (Sweden)

    Grigore Dinu Mοș

    2016-03-01

    Full Text Available From the perspective of man’s relation to the transcendent God, a central concept in the thought of father Dumitru Stăniloae is that of “transcending”, of self-transcendence, of man going beyond himself towards his neighbours and towards his deeper self, towards the mystery of the world and of existence in general, culminating with the fundamental act of transcending towards the divine Absolute. He uses this concept in almost all areas of theology: gnoseology, anthropology, cosmology, ecclesiology, mysteriology, eschatology, spirituality, as well as when discussing ideas of important existentialist and personalist philosophers of the 20th century. According to Stăniloae, God’s transcendence reveals itself as holiness, while Christ, the God-Man, who makes possible man’s convergent and unitary act of transcending, is the “true transcendence”. The real correspondence between transcendent and transcendental emphasizes the Christological foundation of Christian anthropology. For father Stăniloae, man’s self-transcendence is determined by his attraction towards the divine Absolute, as well as by his lack of fulfilment in this world. Monotony is defined as the absence of transcendence, hell – as the impossibility of transcending, and pride as a negative and delusive transcendence. The mystery is a sign of the Transcendent, while man is characterised by an endless act of transcending towards his own mystery, enlightened by the mystery of God. Words and logoi are means of transcending which urge us to purify our mind and to act immediately. The necessity and meaning of the act of transcending are emphasized by the image of the Cross, which makes the world transparent, revealing its Creator. According to Stăniloae, man is a being which transcends time through repentance and hope, while the Church is the immanent which incorporates the transcendent. Moreover, he sees the Holy Sacraments as steps in the act of transcending from the

  5. Chemical Structure and Dynamics annual report 1997

    Energy Technology Data Exchange (ETDEWEB)

    Colson, S.D.; McDowell, R.S.

    1998-03-01

    The Chemical Structure and Dynamics (CS and D) program is a major component of the William R. Wiley Environmental Molecular Sciences Laboratory (EMSL), developed by Pacific Northwest National Laboratory (PNNL) to provide a state-of-the-art collaborative facility for studies of chemical structure and dynamics. The authors respond to the need for a fundamental, molecular level understanding of chemistry at a wide variety of environmentally important interfaces by: (1) extending the experimental characterization and theoretical description of chemical reactions to encompass the effects of condensed media and interfaces; (2) developing a multidisciplinary capability for describing interfacial chemical processes within which the new knowledge generated can be brought to bear on complex phenomena in environmental chemistry and in nuclear waste processing and storage; and (3) developing state-of-the-art analytical methods for characterizing complex materials of the types found in stored wastes and contaminated soils, and for detecting and monitoring trace atmospheric species. The focus of the research is defined primarily by DOE`s environmental problems: fate and transport of contaminants in the subsurface environment, processing and storage of waste materials, cellular effects of chemical and radiological insult, and atmospheric chemistry as it relates to air quality and global change. Twenty-seven projects are described under the following topical sections: Reaction mechanisms at interfaces; High-energy processes at environmental interfaces; Cluster models of the condensed phase; and Miscellaneous.

  6. Reactive chemical dynamics through conical intersections

    Indian Academy of Sciences (India)

    S Ghosal; B Jayachander Rao; S Mahapatra

    2007-09-01

    Reaction dynamics of prototypical, D + H2 and Cl (2P) + H2, chemical reactions occurring through the conical intersections of the respective coupled multi-sheeted potential energy surfaces is examined here. In addition to the electronic coupling, nonadiabatic effects due to relativistic spin-orbit coupling are also considered for the latter reaction. A time-dependent wave packet propagation approach is undertaken and the quantum dynamical observables viz., energy resolved reaction probabilities, integral reaction cross-sections and thermal rate constants are reported.

  7. The Transcendence Degree over a Ring

    CERN Document Server

    Kemper, Gregor

    2011-01-01

    For a finitely generated algebra over a field, the transcendence degree is known to be equal to the Krull dimension. The aim of this paper is to generalize this result to algebras over rings. A new definition of the transcendence degree of an algebra A over a ring R is given by calling elements of A algebraically dependent if they satisfy an algebraic equation over R whose trailing coefficient, with respect to some monomial ordering, is 1. The main result is that for a finitely generated algebra over a Noetherian Jacobson ring, the transcendence degree is equal to the Krull dimension.

  8. Neural Networks in Chemical Reaction Dynamics

    CERN Document Server

    Raff, Lionel; Hagan, Martin

    2011-01-01

    This monograph presents recent advances in neural network (NN) approaches and applications to chemical reaction dynamics. Topics covered include: (i) the development of ab initio potential-energy surfaces (PES) for complex multichannel systems using modified novelty sampling and feedforward NNs; (ii) methods for sampling the configuration space of critical importance, such as trajectory and novelty sampling methods and gradient fitting methods; (iii) parametrization of interatomic potential functions using a genetic algorithm accelerated with a NN; (iv) parametrization of analytic interatomic

  9. Chemical structure and dynamics. Annual report 1994

    Energy Technology Data Exchange (ETDEWEB)

    Colson, S.D.

    1995-07-01

    The Chemical Structure and Dynamics program was organized as a major component of Pacific Northwest Laboratory`s Environmental and Molecular Sciences Laboratory (EMSL), a state-of-the-art collaborative facility for studies of chemical structure and dynamics. Our program responds to the need for a fundamental, molecular-level understanding of chemistry at the wide variety of environmentally important interfaces by (1) extending the experimental characterization and theoretical description of chemical reactions to encompass the effects of condensed media and interfaces, and (2) developing a multidisciplinary capability for describing interfacial chemical processes within which the new knowledge generated can be brought to bear on complex phenomena in environmental chemistry and in nuclear waste processing and storage. This research effort was initiated in 1989 and will continue to evolve over the next few years into a program of rigorous studies of fundamental molecular processes in model systems, such as well-characterized surfaces, single-component solutions, clusters, and biological molecules; and studies of complex systems found in the environment (multispecies, multiphase solutions; solid/liquid, liquid/liquid, and gas/surface interfaces; colloidal dispersions; ultrafine aerosols; and functioning biological systems). The success of this program will result in the achievement of a quantitative understanding of chemical reactions at interfaces, and more generally in condensed media, that is comparable to that currently available for gas-phase reactions. This understanding will form the basis for the development of a priori theories for predictions of macroscopic chemical behavior in condensed and heterogeneous media, adding significantly to the value of field-scale environmental models, the prediction of short- and long-term nuclear waste storage stabilities, and other problems related to the primary missions of the DOE.

  10. Annual Report 1998: Chemical Structure and Dynamics

    Energy Technology Data Exchange (ETDEWEB)

    SD Colson; RS McDowell

    1999-05-10

    The Chemical Structure and Dynamics (CS&D) program is a major component of the William R. Wiley Environmental Molecular Sciences Labo- ratory (EMSL), developed by Pacific Northwest National Laboratory (PNNL) to provide a state-of- the-art collaborative facility for studies of chemical structure and dynamics. We respond to the need for a fundamental, molecular-level understanding of chemistry at a wide variety of environmentally important interfaces by (1) extending the experimental characterization and theoretical description of chemical reactions to encompass the effects of condensed media and interfaces; (2) developing a multidisciplinary capability for describing interracial chemical processes within which the new knowledge generated can be brought to bear on complex phenomena in envi- ronmental chemistry and in nuclear waste proc- essing and storage; and (3) developing state-of- the-art analytical methods for characterizing com- plex materials of the types found in stored wastes and contaminated soils, and for detecting and monitoring trace atmospheric species. Our program aims at achieving a quantitative understanding of chemical reactions at interfaces and, more generally, in condensed media, compa- rable to that currently available for gas-phase reactions. This understanding will form the basis for the development of a priori theories for pre- dicting macroscopic chemical behavior in con- densed and heterogeneous media, which will add significantly to the value of field-scale envi- ronmental models, predictions of short- and long- term nuclear waste storage stabilities, and other areas related to the primary missions of the U.S. Department of Energy (DOE).

  11. Synchronization Dynamics of Coupled Chemical Oscillators

    Science.gov (United States)

    Tompkins, Nathan

    The synchronization dynamics of complex networks have been extensively studied over the past few decades due to their ubiquity in the natural world. Prominent examples include cardiac rhythms, circadian rhythms, the flashing of fireflies, predator/prey population dynamics, mammalian gait, human applause, pendulum clocks, the electrical grid, and of the course the brain. Detailed experiments have been done to map the topology of many of these systems and significant advances have been made to describe the mathematics of these networks. Compared to these bodies of work relatively little has been done to directly test the role of topology in the synchronization dynamics of coupled oscillators. This Dissertation develops technology to examine the dynamics due to topology within networks of discrete oscillatory components. The oscillatory system used here consists of the photo-inhibitable Belousov-Zhabotinsky (BZ) reaction water-in-oil emulsion where the oscillatory drops are diffusively coupled to one another and the topology is defined by the geometry of the diffusive connections. Ring networks are created from a close-packed 2D array of drops using the Programmable Illumination Microscope (PIM) in order to test Turing's theory of morphogenesis directly. Further technology is developed to create custom planar networks of BZ drops in more complicated topologies which can be individually perturbed using illumination from the PIM. The work presented here establishes the validity of using the BZ emulsion system with a PIM to study the topology induced effects on the synchronization dynamics of coupled chemical oscillators, tests the successes and limitations of Turing's theory of morphogenesis, and develops new technology to further probe the effects of network topology on a system of coupled oscillators. Finally, this Dissertation concludes by describing ongoing experiments which utilize this new technology to examine topology induced transitions of synchronization

  12. The Chemical Evolution of Dynamically Hot Galaxies

    Directory of Open Access Journals (Sweden)

    Michael G. Richer

    2001-01-01

    Full Text Available We investigate the chemical properties of M32, the bulges of M31 and the Milky Way, and the dwarf spheroidal galaxies NGC 205, NGC 185, Sagittarius, and Fornax using oxygen abundances for their planetary nebulae. Our principal result is that the mean stellar oxygen abundances correlate very well with thei r mean velocity dispersions, implying that the balance between energy input from type II supernovae and the gravitational potential controls chemical evolution in bulges, ellipticals, and dwarf spheroidals. It appears that chemical evolution ceases once supernovae have injected sufficient energy that a galacti c wind develops. All of the galaxies follow a single relation between oxygen abundance and luminosity, but the dwarf spheroidals have systematically higher [O/Fe] ratios than the other galaxies. Consequently, dynamically hot galaxies do not share a common star formation history nor need to a common chemical evolution, despite attaining similar mean stellar oxygen abundances when formin g similar masses. The oxygen abundances support previous indications that stars in higher luminosity ellipticals and bulges were formed on a shorter time scale than their counterparts in less luminous systems.

  13. Theoretical studies of chemical reaction dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Schatz, G.C. [Argonne National Laboratory, IL (United States)

    1993-12-01

    This collaborative program with the Theoretical Chemistry Group at Argonne involves theoretical studies of gas phase chemical reactions and related energy transfer and photodissociation processes. Many of the reactions studied are of direct relevance to combustion; others are selected they provide important examples of special dynamical processes, or are of relevance to experimental measurements. Both classical trajectory and quantum reactive scattering methods are used for these studies, and the types of information determined range from thermal rate constants to state to state differential cross sections.

  14. The chemical bond structure and dynamics

    CERN Document Server

    Zewail, Ahmed

    1992-01-01

    This inspired book by some of the most influential scientists of our time--including six Nobel laureates--chronicles our emerging understanding of the chemical bond through the last nine decades and into the future. From Pauling's early structural work using x-ray and electron diffraction to Zewail's femtosecond lasers that probe molecular dynamics in real time; from Crick's molecular biology to Rich's molecular recognition, this book explores a rich tradition of scientific heritage and accomplishment. The perspectives given by Pauling, Perutz, Rich, Crick, Porter, Polanyi, Herschbach, Zewail,

  15. Application of synchrotron radiation in chemical dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Heimann, P.; Koike, M.; Kung, A.H.; Ng, C.Y.; White, M.G.; Wodtke, A.

    1993-05-01

    In October 1992, funding was approved to begin construction of a beamline and two end stations to support chemical dynamics experiments at LBL's Advanced Light Source (ALS). This workshop was organized to develop specifications and plans and to select a working team to design and supervise the construction project. Target date for starting the experiments is January 1995. Conclusions of the workshop and representative experiments proposed in earlier workshops to form the basis for beamline plans and end-station designs are summarized in this report. 6 figs.

  16. Application of synchrotron radiation in chemical dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Heimann, P.; Koike, M.; Kung, A.H.; Ng, C.Y.; White, M.G.; Wodtke, A.

    1993-05-01

    In October 1992, funding was approved to begin construction of a beamline and two end stations to support chemical dynamics experiments at LBL`s Advanced Light Source (ALS). This workshop was organized to develop specifications and plans and to select a working team to design and supervise the construction project. Target date for starting the experiments is January 1995. Conclusions of the workshop and representative experiments proposed in earlier workshops to form the basis for beamline plans and end-station designs are summarized in this report. 6 figs.

  17. Transgressions and Transcendence: Surpassing Disciplinary Boundaries.

    Science.gov (United States)

    Wughalter, Emily H.

    2002-01-01

    Discusses how women such as Amy Morris Homans, Susan B. Anthony, Elizabeth Cady Stanton, and Mary Wollstonecraft transgressed boundaries, allowing others to transcend old boundary limitations in physical education, examining the Boston Normal School of Gymnastics established for training women as directors of physical education over 100 years ago…

  18. Quantum dynamics of fast chemical reactions

    Energy Technology Data Exchange (ETDEWEB)

    Light, J.C. [Univ. of Chicago, IL (United States)

    1993-12-01

    The aims of this research are to explore, develop, and apply theoretical methods for the evaluation of the dynamics of gas phase collision processes, primarily chemical reactions. The primary theoretical tools developed for this work have been quantum scattering theory, both in time dependent and time independent forms. Over the past several years, the authors have developed and applied methods for the direct quantum evaluation of thermal rate constants, applying these to the evaluation of the hydrogen isotopic exchange reactions, applied wave packet propagation techniques to the dissociation of Rydberg H{sub 3}, incorporated optical potentials into the evaluation of thermal rate constants, evaluated the use of optical potentials for state-to-state reaction probability evaluations, and, most recently, have developed quantum approaches for electronically non-adiabatic reactions which may be applied to simplify calculations of reactive, but electronically adiabatic systems. Evaluation of the thermal rate constants and the dissociation of H{sub 3} were reported last year, and have now been published.

  19. Experiences on dynamic simulation software in chemical engineering education

    OpenAIRE

    Komulainen, Tiina M.; Enemark-Rasmussen, Rasmus; Sin, Gürkan; John P Fletcher; Cameron, David

    2012-01-01

    Commercial process simulators are increasing interest in the chemical engineer education. In this paper, the use of commercial dynamic simulation software, D-SPICE® and K-Spice®, for three different chemical engineering courses is described and discussed. The courses cover the following topics: basic chemical engineering, operability and safety analysis and process control. User experiences from both teachers and students are presented. The benefits of dynamic simulation as an additional teac...

  20. Some Reflections on Logic and Transcendence

    DEFF Research Database (Denmark)

    Øhrstrøm, Peter

    2010-01-01

    of naturalism and even the existence of God provided that certain basic assumptions are taken for granted. In this paper, I shall consider these arguments, and I shall show that there are valid versions of these arguments. However, it will also be demonstrated that it will be possible for the atheist to find......It is sometimes argued that the very existence of a notion of validity of logical inference on which all rational persons should agree is an indication of the existence of something transcendent. It has also been argued that logic can be used in order to demonstrate the problematic status...... a way out, since all the arguments pointing to the existence of something transcendent are based on premises, which may in principle be rejected. The atheist must, however, take the validity of these arguments into account, when he seeks to establish his worldview – assuming that he wants his worldview...

  1. In your face: Transcendence in embodied interaction

    Directory of Open Access Journals (Sweden)

    Shaun eGallagher

    2014-07-01

    Full Text Available In cognitive psychology, studies concerning the face tend to focus on questions about face recognition, theory of mind and empathy. Questions about the face, however, also fit into a very different set of issues that are central to ethics. Based especially on the work of Levinas, philosophers have come to see that reference to the face of another person can anchor conceptions of moral responsibility and ethical demand. Levinas points to a certain irreducibility and transcendence implicit in the face of the other. In this paper I argue that the notion of transcendence involved in this kind of analysis can be given a naturalistic interpretation by drawing on recent interactive approaches to social cognition found in developmental psychology, phenomenology, and the study of autism.

  2. Love's Transcendence and the Problem of Theodicy

    DEFF Research Database (Denmark)

    Welz, Claudia

    's transcendence in human movements of self-transcendence. Moreover, they have remarkable contributions to the current debates on ‘metaphysics of presence' and ‘onto-theology' - debates dealing with the limits of Husserl's and Heidegger's phenomenology. In dialogue with Levinas, the presence of God's love......, their reasons for having no reason to defend God and their ethics of love are discussed ‘between' German idealism and French phenomenology. Both of them follow Kant's practical turn of the problem of theodicy, oppose Hegel's theodicy through history and anticipate Levinas' idea to look for the traces of God...... is in question, in dialogue with Derrida God's presence as a gift, and in dialogue with Marion the gift of God's presence as a so-called ‘saturated' self-giving phenomenon. In conclusion to these discussions, theology is developed as semiotic phenomenology of the Invisible....

  3. In your face: transcendence in embodied interaction.

    Science.gov (United States)

    Gallagher, Shaun

    2014-01-01

    In cognitive psychology, studies concerning the face tend to focus on questions about face recognition, theory of mind (ToM) and empathy. Questions about the face, however, also fit into a very different set of issues that are central to ethics. Based especially on the work of Levinas, philosophers have come to see that reference to the face of another person can anchor conceptions of moral responsibility and ethical demand. Levinas points to a certain irreducibility and transcendence implicit in the face of the other. In this paper I argue that the notion of transcendence involved in this kind of analysis can be given a naturalistic interpretation by drawing on recent interactive approaches to social cognition found in developmental psychology, phenomenology, and the study of autism.

  4. Chemical Dynamics, Molecular Energetics, and Kinetics at the Synchrotron

    Energy Technology Data Exchange (ETDEWEB)

    Leone, Stephen R.; Ahmed, Musahid; Wilson, Kevin R.

    2010-03-14

    Scientists at the Chemical Dynamics Beamline of the Advanced Light Source in Berkeley are continuously reinventing synchrotron investigations of physical chemistry and chemical physics with vacuum ultraviolet light. One of the unique aspects of a synchrotron for chemical physics research is the widely tunable vacuum ultraviolet light that permits threshold ionization of large molecules with minimal fragmentation. This provides novel opportunities to assess molecular energetics and reaction mechanisms, even beyond simple gas phase molecules. In this perspective, significant new directions utilizing the capabilities at the Chemical Dynamics Beamline are presented, along with an outlook for future synchrotron and free electron laser science in chemical dynamics. Among the established and emerging fields of investigations are cluster and biological molecule spectroscopy and structure, combustion flame chemistry mechanisms, radical kinetics and product isomer dynamics, aerosol heterogeneous chemistry, planetary and interstellar chemistry, and secondary neutral ion-beam desorption imaging of biological matter and materials chemistry.

  5. Experiences on dynamic simulation software in chemical engineering education

    DEFF Research Database (Denmark)

    Komulainen, Tiina M.; Enemark-rasmussen, Rasmus; Sin, Gürkan

    2012-01-01

    Commercial process simulators are increasing interest in the chemical engineer education. In this paper, the use of commercial dynamic simulation software, D-SPICE® and K-Spice®, for three different chemical engineering courses is described and discussed. The courses cover the following topics......: basic chemical engineering, operability and safety analysis and process control. User experiences from both teachers and students are presented. The benefits of dynamic simulation as an additional teaching tool are discussed and summarized. The experiences confirm that commercial dynamic simulators...

  6. Dynamic Reaction Figures: An Integrative Vehicle for Understanding Chemical Reactions

    Science.gov (United States)

    Schultz, Emeric

    2008-01-01

    A highly flexible learning tool, referred to as a dynamic reaction figure, is described. Application of these figures can (i) yield the correct chemical equation by simply following a set of menu driven directions; (ii) present the underlying "mechanism" in chemical reactions; and (iii) help to solve quantitative problems in a number of different…

  7. Catalysis of Dynamical Chiral Symmetry Breaking by Chiral Chemical Potential

    CERN Document Server

    Braguta, V V

    2016-01-01

    In this paper we study the properties of media with chiral imbalance parameterized by chiral chemical potential. It is shown that depending on the strength of interaction between constituents in the media the chiral chemical potential either creates or enhances dynamical chiral symmetry breaking. Thus the chiral chemical potential plays a role of the catalyst of dynamical chiral symmetry breaking. Physically this effect results from the appearance of the Fermi surface and additional fermion states on this surface which take part in dynamical chiral symmetry breaking. An interesting conclusion which can be drawn is that at sufficiently small temperature chiral plasma is unstable with respect to condensation of Cooper pairs and dynamical chiral symmetry breaking even for vanishingly small interactions between constituents.

  8. Laboratory chemical dynamics and outer planets

    Science.gov (United States)

    Kaiser, Ralf I.

    Reactions of CN (2Σ+) and C2H (2Σ+) radicals with unsaturated hydrocarbons are of fundamental relevance to form complex nitriles and polyynes in hydrocarbon rich atmospheres, planets, and moons. Here we present results on crossed molecular beams experiments combined with electronic structure calculations on the reactions of C2H and CN radicals with acetylene, methylacetylene, allene, and benzene. Our investigation show that both radicals attack the unsaturated bond without entrance barrier in exothermic reactions. The collision complex decomposes to form the hydrocarbon and a H atom or shows a H atom migration prior to hydrogen atom loss. The identification of this C2H /CN - H exchange opens a versatile route to form unsaturated nitriles and polyynes and predicts their formation in hydrocarbon rich planetary atmospheres. Further, our studies provide a solid database on reaction products and shall guide chemical investigation of the NASA-ESA Cassini-Huygens mission to identify unsaturated hydrocarbons in Titan. Most important, these experiments verify unambiguously that the knowledge of reaction rate constants only is insufficient for detailed chemical models of planetary atmospheres. Reaction products and most important reactive intermediates MUST be included to get a plausible chemical model of planetary atmospheres.

  9. Wounded Leader: An Archetypal Embodiment of Compassionate Transcendent Leadership

    Science.gov (United States)

    Mears, Kathryn

    2009-01-01

    The purpose of this study was to seek to further the formation of the emerging transcendent leadership model by exploring the archetypal image identified as wounded leader. The wounded leader archetype is introduced as a leadership style of influence that fits well within the framework of the transcendent leadership model. This study…

  10. Transcending chronic liver disease: a qualitative study.

    Science.gov (United States)

    Wainwright, S P

    1997-01-01

    This study explores and describes experiences of chronic liver disease from the patient's perspective. No qualitative research studies appear to have examined the experiences of these patients. In-depth focused interviews and grounded theory data collection and data analysis methods were used. A two-stage theoretical framework (becoming ill, and not living) of the experience of transcending chronic liver disease is presented. Sociological and psychological literature on common sense models of health and illness are briefly reviewed. Several suggestions for further research are made. The way in which this qualitative research study is leading to a quantitative and qualitative appraisal of the psychological adjustment in end-stage chronic liver disease patients is outlined.

  11. NATO Advanced Study Institute on Advances in Chemical Reaction Dynamics

    CERN Document Server

    Capellos, Christos

    1986-01-01

    This book contains the formal lectures and contributed papers presented at the NATO Advanced Study Institute on. the Advances in Chemical Reaction Dynamics. The meeting convened at the city of Iraklion, Crete, Greece on 25 August 1985 and continued to 7 September 1985. The material presented describes the fundamental and recent advances in experimental and theoretical aspects of, reaction dynamics. A large section is devoted to electronically excited states, ionic species, and free radicals, relevant to chemical sys­ tems. In addition recent advances in gas phase polymerization, formation of clusters, and energy release processes in energetic materials were presented. Selected papers deal with topics such as the dynamics of electric field effects in low polar solutions, high electric field perturbations and relaxation of dipole equilibria, correlation in picosecond/laser pulse scattering, and applications to fast reaction dynamics. Picosecond transient Raman spectroscopy which has been used for the elucidati...

  12. Glucans monomer-exchange dynamics as an open chemical network

    Energy Technology Data Exchange (ETDEWEB)

    Rao, Riccardo, E-mail: riccardo.rao@uni.lu; Esposito, Massimiliano, E-mail: massimiliano.esposito@uni.lu [Complex Systems and Statistical Mechanics, Physics and Materials Science Research Unit, University of Luxembourg, L-1511 Luxembourg (Luxembourg); Lacoste, David [Laboratoire de Physico-Chimie Théorique, UMR CNRS Gulliver 7083, ESPCI - 10 rue Vauquelin, F-75231 Paris (France)

    2015-12-28

    We describe the oligosaccharides-exchange dynamics performed by the so-called D-enzymes on polysaccharides. To mimic physiological conditions, we treat this process as an open chemical network by assuming some of the polymer concentrations fixed (chemostatting). We show that three different long-time behaviors may ensue: equilibrium states, nonequilibrium steady states, and continuous growth states. We dynamically and thermodynamically characterize these states and emphasize the crucial role of conservation laws in identifying the chemostatting conditions inducing them.

  13. Glucans monomer-exchange dynamics as an open chemical network

    CERN Document Server

    Rao, Riccardo; Esposito, Massimiliano

    2015-01-01

    We describe the oligosaccharides-exchange dynamics performed by so-called D-enzymes on polysaccharides. To mimic physiological conditions, we treat this process as an open chemical network by assuming some of the polymer concentrations fixed (chemostatting). We show that three different long-time behaviors may ensue: equilibrium states, nonequilibrium steady states, and continuous growth states. We dynamically and thermodynamically characterize these states and emphasize the crucial role of conservation laws in identifying the chemostatting conditions inducing them.

  14. Chemical dynamics in the gas phase: Time-dependent quantum mechanics of chemical reactions

    Energy Technology Data Exchange (ETDEWEB)

    Gray, S.K. [Argonne National Laboratory, IL (United States)

    1993-12-01

    A major goal of this research is to obtain an understanding of the molecular reaction dynamics of three and four atom chemical reactions using numerically accurate quantum dynamics. This work involves: (i) the development and/or improvement of accurate quantum mechanical methods for the calculation and analysis of the properties of chemical reactions (e.g., rate constants and product distributions), and (ii) the determination of accurate dynamical results for selected chemical systems, which allow one to compare directly with experiment, determine the reliability of the underlying potential energy surfaces, and test the validity of approximate theories. This research emphasizes the use of recently developed time-dependent quantum mechanical methods, i.e. wave packet methods.

  15. Dynamical mean-field theory from a quantum chemical perspective.

    Science.gov (United States)

    Zgid, Dominika; Chan, Garnet Kin-Lic

    2011-03-07

    We investigate the dynamical mean-field theory (DMFT) from a quantum chemical perspective. Dynamical mean-field theory offers a formalism to extend quantum chemical methods for finite systems to infinite periodic problems within a local correlation approximation. In addition, quantum chemical techniques can be used to construct new ab initio Hamiltonians and impurity solvers for DMFT. Here, we explore some ways in which these things may be achieved. First, we present an informal overview of dynamical mean-field theory to connect to quantum chemical language. Next, we describe an implementation of dynamical mean-field theory where we start from an ab initio Hartree-Fock Hamiltonian that avoids double counting issues present in many applications of DMFT. We then explore the use of the configuration interaction hierarchy in DMFT as an approximate solver for the impurity problem. We also investigate some numerical issues of convergence within DMFT. Our studies are carried out in the context of the cubic hydrogen model, a simple but challenging test for correlation methods. Finally, we finish with some conclusions for future directions.

  16. The immanence and transcendence of God in Adamic incarnational Christology: An African ethical reflection for the public

    Directory of Open Access Journals (Sweden)

    Vhumani Magezi

    2016-03-01

    Full Text Available This article argues that the transcendence and immanence of God amplified in Christ should influence African believers� private and public ethics. It accomplishes this by engaging transcendence and immanence of God in the traditional African worldview. The African traditional worldview in many respects believes the transcendent God whose immanence is mediated by lesser spiritual intermediary powers. In responding to this view of God�s transcendence and immanence, we discuss the amplified transcendence and immanence of God in the Adamic incarnational Christological model. This model argues that in the incarnation, God�s transcendence and immanence is amplified by his assumption of our human mode of existence as the New Adam for our redemption. That is, even though God has always been transcendent and present within his creation before the incarnation, his immanence within humanity is amplified by God becoming man in and through Jesus Christ as the New Adam. The ascension of Jesus Christ does not diminish God�s presence within Christians. God continues to have his personal presence within believers through the dynamic presence of the Holy Spirit among them. The transcendence and immanence of God (amplified in Christ therefore is brought to bear in the private and public ethics of Christians. In contrast to the limited immanence of human beings, God�s immanence is infinite. That is, there is nothing human beings can do which is outside of God�s reach and knowledge. It is from this perspective that African Christians are encouraged to live lives conscious of the infinite-immanent God, who sees both their private and public lives. The private and public life of believers should resemble God�s character and behaviour demonstrated by Jesus Christ, God incarnate, in his earthly ministry. Thus, the transcendence and immanence of God amplified in Christ influences African believers to live as the true ambassadors of Christ who exhibit

  17. Molecular Dynamics Simulations of Solutions at Constant Chemical Potential

    CERN Document Server

    Perego, Claudio; Parrinello, Michele

    2015-01-01

    Molecular Dynamics studies of chemical processes in solution are of great value in a wide spectrum of applications, that range from nano-technology to pharmaceutical chemistry. However, these calculations are affected by severe finite-size effects, such as the solution being depleted as the chemical process proceeds, that influence the outcome of the simulations. To overcome these limitations, one must allow the system to exchange molecules with a macroscopic reservoir, thus sampling a Grand-Canonical ensemble. Despite the fact that different remedies have been proposed, this still represents a key challenge in molecular simulations. In the present work we propose the C$\\mu$MD method, which introduces an external force that controls the environment of the chemical process of interest. This external force, drawing molecules from a finite reservoir, maintains the chemical potential constant in the region where the process takes place. We have applied the C$\\mu$MD method to the paradigmatic case of urea crystall...

  18. GAS PHASE MOLECULAR DYNAMICS: HIGH-RESOLUTION SPECTROSCOPIC PROBES OF CHEMICAL DYNAMICS.

    Energy Technology Data Exchange (ETDEWEB)

    HALL, G.E.

    2006-05-30

    This research is carried out as part of the Gas Phase Molecular Dynamics group program in the Chemistry Department at Brookhaven National Laboratory. High-resolution spectroscopic tools are developed and applied to problems in chemical dynamics. Recent topics have included the state-resolved studies of collision-induced electronic energy transfer, dynamics of barrierless unimolecular reactions, and the kinetics and spectroscopy of transient species.

  19. Transcendence, religion and spirituality in medicine

    Science.gov (United States)

    Rassoulian, Anahita; Seidman, Charles; Löffler-Stastka, Henriette

    2016-01-01

    Abstract To explore how medical students—the doctors of tomorrow—reflect upon meeting the spiritual needs of their patients, and whether they have reflected on their own religious or spiritual beliefs, or not. The study also investigates to what extent the students feel comfortable with addressing spiritual issues in their patient care, and whether they feel this is beyond their role as medical doctors. A self-administered questionnaire was developed. The survey was administered in teaching classes at the medical university of Vienna. One thousand four hundred (836 women and 564 men) students responded, laying the foundation for a thorough statistical analysis. 59.5% of the students had reflected on their own belief concepts, 21.9% consider themselves religious, and 20.1% see themselves as spiritual individuals. 75.6% of the students agreed with the statement that religious conviction/spirituality might have an effect on how cancer patients cope. 85.9% would consider talking with their patients about religious/spiritual issues if patients wish to do so. 86.3% would involve chaplains if they feel it is necessary. The results of this study suggest that future doctors want to see the patient in a wider scope than the bio-psycho-social one, by including the meta-dimension of transcendence. PMID:27661053

  20. 2-D Chemical-Dynamical Modeling of Venus's Sulfur Variability

    Science.gov (United States)

    Bierson, Carver J.; Zhang, Xi

    2016-10-01

    Over the last decade a combination of ground based and Venus Express observations have been made of the concentration of sulfur species in Venus's atmosphere, both above [1, 2] and below the clouds [3, 4]. These observations put constraints on both the vertical and meridional variations of the major sulfur species in Venus's atmosphere.. It has also been observed that SO2 concentrations varies on both timescales of hours and years [1,4]. The spatial and temporal distribution of tracer species is owing to two possibilities: mutual chemical interaction and dynamical tracer transport.Previous Chemical modeling of Venus's middle atmosphere has only been explored in 1-D. We will present the first 2-D (altitude and latitude) chemical-dynamical model for Venus's middle atmosphere. The sulfur chemistry is based on of the 1D model of Zhang et al. 2012 [5]. We do model runs over multiple Venus decades testing two scenarios: first one with varying sulfur fluxes from below, and second with secular dynamical perturbations in the atmosphere [6]. By comparing to Venus Express and ground based observations, we put constraints on the dynamics of Venus's middle atmosphere.References: [1] Belyaev et al. Icarus 2012 [2] Marcq et al. Nature geoscience, 2013 [3] Marcq et al. JGR:Planets, 2008 [4] Arney et al. JGR:Planets, 2014 [5] Zhang et al. Icarus 2012 [6] Parish et al. Icarus 2012

  1. Surprised by Bird, Bard, and Bach: Language, Silence, and Transcendence.

    Science.gov (United States)

    Suhor, Charles

    1991-01-01

    Argues the importance of the relationships among silence and literature, the arts, and other experiences that point toward transcendence. Suggests that English teachers can expand the repertoire of classroom activities and teaching techniques that make use of silence. (KEH)

  2. The hunt for the dynamical resonances in chemical reaction dynamics: a perspective on historical advances

    Directory of Open Access Journals (Sweden)

    Yu Angyang

    2015-06-01

    Full Text Available The theoretical background and basic definition of the resonances in chemical reaction dynamics have been introduced in this article. The historical breakthrough in the experimental search for the reaction resonances has been reviewed in this report, with an emphasis on the crossed molecular beam apparatus. The research of the chemical reaction resonances has attracted many scientists’ attention from 80s of last century. The chemical reaction resonances in the F+H2 reaction were firstly observed by the researchers of the Chinese Academy of Sciences in 2006. Besides, the partial wave resonances in the chemical reactions have been observed for the first time in 2010.

  3. Coriolis coupling and nonadiabaticity in chemical reaction dynamics.

    Science.gov (United States)

    Wu, Emilia L

    2010-12-01

    The nonadiabatic quantum dynamics and Coriolis coupling effect in chemical reaction have been reviewed, with emphasis on recent progress in using the time-dependent wave packet approach to study the Coriolis coupling and nonadiabatic effects, which was done by K. L. Han and his group. Several typical chemical reactions, for example, H+D(2), F+H(2)/D(2)/HD, D(+)+H(2), O+H(2), and He+H(2)(+), have been discussed. One can find that there is a significant role of Coriolis coupling in reaction dynamics for the ion-molecule collisions of D(+)+H(2), Ne+H(2)(+), and He+H(2)(+) in both adiabatic and nonadiabatic context.

  4. Dynamics of prebiotic RNA reproduction illuminated by chemical game theory.

    Science.gov (United States)

    Yeates, Jessica A M; Hilbe, Christian; Zwick, Martin; Nowak, Martin A; Lehman, Niles

    2016-05-03

    Many origins-of-life scenarios depict a situation in which there are common and potentially scarce resources needed by molecules that compete for survival and reproduction. The dynamics of RNA assembly in a complex mixture of sequences is a frequency-dependent process and mimics such scenarios. By synthesizing Azoarcus ribozyme genotypes that differ in their single-nucleotide interactions with other genotypes, we can create molecules that interact among each other to reproduce. Pairwise interplays between RNAs involve both cooperation and selfishness, quantifiable in a 2 × 2 payoff matrix. We show that a simple model of differential equations based on chemical kinetics accurately predicts the outcomes of these molecular competitions using simple rate inputs into these matrices. In some cases, we find that mixtures of different RNAs reproduce much better than each RNA type alone, reflecting a molecular form of reciprocal cooperation. We also demonstrate that three RNA genotypes can stably coexist in a rock-paper-scissors analog. Our experiments suggest a new type of evolutionary game dynamics, called prelife game dynamics or chemical game dynamics. These operate without template-directed replication, illustrating how small networks of RNAs could have developed and evolved in an RNA world.

  5. Chemical memory reactions induced bursting dynamics in gene expression.

    Science.gov (United States)

    Tian, Tianhai

    2013-01-01

    Memory is a ubiquitous phenomenon in biological systems in which the present system state is not entirely determined by the current conditions but also depends on the time evolutionary path of the system. Specifically, many memorial phenomena are characterized by chemical memory reactions that may fire under particular system conditions. These conditional chemical reactions contradict to the extant stochastic approaches for modeling chemical kinetics and have increasingly posed significant challenges to mathematical modeling and computer simulation. To tackle the challenge, I proposed a novel theory consisting of the memory chemical master equations and memory stochastic simulation algorithm. A stochastic model for single-gene expression was proposed to illustrate the key function of memory reactions in inducing bursting dynamics of gene expression that has been observed in experiments recently. The importance of memory reactions has been further validated by the stochastic model of the p53-MDM2 core module. Simulations showed that memory reactions is a major mechanism for realizing both sustained oscillations of p53 protein numbers in single cells and damped oscillations over a population of cells. These successful applications of the memory modeling framework suggested that this innovative theory is an effective and powerful tool to study memory process and conditional chemical reactions in a wide range of complex biological systems.

  6. Solution of Chemical Dynamic Optimization Using the Simultaneous Strategies

    Institute of Scientific and Technical Information of China (English)

    LIU Xinggao; CHEN Long; HU Yunqing

    2013-01-01

    An approach of simultaneous strategies with two novel techniques is proposed to improve the solution accuracy of chemical dynamic optimization problems.The first technique is to handle constraints on control variables based on the finite-element collocation so as to control the approximation error for discrete optimal problems,where a set of control constraints at element knots are integrated with the procedure for optimization leading to a significant gain in the accuracy of the simultaneous strategies.The second technique is to make the mesh refinement more feasible and reliable by introducing length constraints and guideline in designing appropriate element length boundaries,so that the proposed approach becomes more efficient in adjusting elements to track optimal control profile breakpoints and ensure accurate state and control profiles.Four classic benchmarks of dynamic optimization problems are used as illustrations,and the proposed approach is compared with literature reports.The research results reveal that the proposed approach is preferable in improving the solution accuracy of chemical dynamic optimization problem.

  7. The Coupled Chemical and Physical Dynamics Model of MALDI

    Science.gov (United States)

    Knochenmuss, Richard

    2016-06-01

    The coupled physical and chemical dynamics model of ultraviolet matrix-assisted laser desorption/ionization (MALDI) has reproduced and explained a wide variety of MALDI phenomena. The rationale behind and elements of the model are reviewed, including the photophysics, kinetics, and thermodynamics of primary and secondary reaction steps. Experimental results are compared with model predictions to illustrate the foundations of the model, coupling of ablation and ionization, differences between and commonalities of matrices, secondary charge transfer reactions, ionization in both polarities, fluence and concentration dependencies, and suppression and enhancement effects.

  8. DYNSYL: a general-purpose dynamic simulator for chemical processes

    Energy Technology Data Exchange (ETDEWEB)

    Patterson, G.K.; Rozsa, R.B.

    1978-09-05

    Lawrence Livermore Laboratory is conducting a safeguards program for the Nuclear Regulatory Commission. The goal of the Material Control Project of this program is to evaluate material control and accounting (MCA) methods in plants that handle special nuclear material (SNM). To this end we designed and implemented the dynamic chemical plant simulation program DYNSYL. This program can be used to generate process data or to provide estimates of process performance; it simulates both steady-state and dynamic behavior. The MCA methods that may have to be evaluated range from sophisticated on-line material trackers such as Kalman filter estimators, to relatively simple material balance procedures. This report describes the overall structure of DYNSYL and includes some example problems. The code is still in the experimental stage and revision is continuing.

  9. Quantum measurement corrections to chemically induced dynamic nuclear polarization

    CERN Document Server

    Kominis, I K

    2013-01-01

    Chemically induced dynamic nuclear polarization has emerged as a universal signature of spin order in photosynthetic reaction centers. Such polarization, significantly enhanced above thermal equilibrium, is known to result from the nuclear spin sorting inherent in the radical pair mechanism underlying long-lived charge-separated states in photosynthetic reaction centers. We will here show that the recently understood fundamental quantum dynamics of radical-ion-pair reactions open up a new and completely unexpected venue towards obtaining CIDNP signals. The fundamental decoherence mechanism inherent in the recombination process of radical pairs is shown to produce nuclear spin polarizations on the order of $10^4$ times or more higher than thermal equilibrium values at low fields relevant to natural photosynthesis in earth's magnetic field. This opens up the possibility of a fundamentally new exploration of the biological significance of high nuclear polarizations in photosynthesis.

  10. Multiple time scale based reduction scheme for nonlinear chemical dynamics

    Science.gov (United States)

    Das, D.; Ray, D. S.

    2013-07-01

    A chemical reaction is often characterized by multiple time scales governing the kinetics of reactants, products and intermediates. We eliminate the fast relaxing intermediates in autocatalytic reaction by transforming the original system into a new one in which the linearized part is diagonal. This allows us to reduce the dynamical system by identifying the associated time scales and subsequent adiabatic elimination of the fast modes. It has been shown that the reduced system sustains the robust qualitative signatures of the original system and at times the generic form of the return map for the chaotic system from which complex dynamics stems out in the original system can be identified. We illustrate the scheme for a three-variable cubic autocatalytic reaction and four-variable peroxidase-oxidase reaction.

  11. SPH code for dynamical and chemical evolution of disk galaxies

    CERN Document Server

    Berczik, P

    1998-01-01

    The problem of chemical and dynamical evolution of galaxies is one of the most attracting and complex problems of modern astrophysics. Within the framework of the given work the standard dynamic Smoothed Particle Hydrodynamics (SPH) code (Monaghan J.J. 1992, ARAA, 30, 543) is noticeably expanded. Our investigation concernes with the changes and incorporation of new ideas into the algorithmic inclusion of Star Formation (SF) and Super Novae (SN) explosions in SPH (Berczik P. & Kravchuk S.G., 1996, ApSpSci, 245, 27). The proposed energy criterion for definition of a place and efficiency of SF results in the successfully explain Star Formation History (SFH) in isolated galaxies of different types. On the base of original ideas we expand a code in a more realistic way of the description of effects of return of a hot, chemical enriched gas in Interstellar Matter (ISM). In addition to the account of SNII, we offer the self-agreed account of SNIa and PN. This allows to describe not only the ISM content of $ O^{1...

  12. De Magistro: dos signos à transcendência (De magistro: from signs to transcendence

    Directory of Open Access Journals (Sweden)

    Hugo Langone

    2012-03-01

    Full Text Available No De libero arbitrio, a fim de provar que Deus existe, santo Agostinho recorre à demonstração da existência de elementos inteligíveis que são universais, imutáveis e superiores a alma. No entanto, o famoso e longo processo de ascensão encontra ainda outras veredas, e no De magistro o futuro bispo de Hipona chega às realidades metafísicas (e, assim, ao próprio Deus através da análise da linguagem verbal e da comunicação. Partindo das considerações tecidas no próprio tratado, escrito em 389, este artigo pretende analisar como se dá a transcendência da alma no diálogo travado entre santo Agostinho e seu filho Adeodato, e onde se cristalizam as teorias agostinianas do conhecimento e do ensino. Ao fim do trabalho, esperamos tornar manifesta a riqueza do pensamento linguístico do santo – pelo qual podemos vislumbrar suas possíveis contribuições para as mais diversas ramificações da linguística, da filosofia e da teologia – e a sutileza de seu raciocínio. Palavras-chave: Agostinho; Linguagem; Alma; Deus.   Abstract In his On the Free Will, Saint Augustine, willing to prove the existence of God, demonstrates the existence of intelligible elements which are universal, immutable and superior to the soul. Other paths, however, can fulfill this famous and long ascent, and in De magistro the future Bishop of Hippo attains those metaphysical realities (and God himself through the analysis of the verbal language. Thus, this article aims at examining, through the considerations made in the text itself, how the transcendence of the soul occurs in this dialogue between Augustine and his son, Deusdedit, in which his theories on knowledge and learning are consolidated. At the end of our work, we hope to make clear how rich Augustine’s thought is – through which we can note his possible contributions to many ramifications of linguistics, philosophy, and theology – and how subtle are his arguments. Keywords: Augustine

  13. Transcendence, Taxis, Trust: Richard Kearney and Jacques Derrida

    Directory of Open Access Journals (Sweden)

    Ulrich Schmiedel

    2017-03-01

    Full Text Available Whatever else it takes to drive a taxi, it takes trust. Day after day, the driver has to decide whether the other is or is not trustworthy. I take the taxi as a test case to analyze and assess Richard Kearney’s diacritical hermeneutics of the other. I argue that Kearney functionalizes the concept of transcendence in order to connect the transcendence of the finite other to the transcendence of the infinite other. However, in his central critique of the deconstructionists following Jacques Derrida, Kearney counters his connection. While Kearney’s critique of Derrida’s account of absolute alterity is correct and compelling, I argue that Derrida’s critique of a distinction between the trustworthy other and the non-trustworthy other might be more crucial than Kearney contends. Insisting on openness to the other’s otherness, Derrida provokes any hermeneutic of the other to trust in transcendence. The taxi is taken as a test to illustrate the implications which diacritical and deconstructive drivers might have for evaluating the entanglement of ethics and eschatology—inside and outside the taxi.

  14. Multicultural Connections: Using Stories to Transcend Cultural Boundaries in Supervision

    Science.gov (United States)

    Sommer, Carol A.; Derrick, Emily C.; Bourgeois, Marc B.; Ingene, Daphne H.; Yang, Ji Woong; Justice, Cheryl A.

    2009-01-01

    Stories have long been used in various cultures and settings to help make meaning and enhance awareness. The authors describe how reflection on and discussion of myths and fairy tales in supervision may help transcend cultural boundaries and increase multicultural understanding.

  15. Transcending Domesticity:A Biographic Study on Sarah Orne Jewett

    Institute of Scientific and Technical Information of China (English)

    庄义辉

    2013-01-01

      Following Showalter’s division of the three phases in women’s literary history, namely the“Feminine, Feminist and Fe⁃male”, this essay launches a biographic study on Sarah Orne Jewett, discussing how she transcends domesticity by embracing fe⁃male friendship in life and writing a female culture in literature.

  16. Spirituality in Music Education: Transcending Culture, Exploration III

    Science.gov (United States)

    Palmer, Anthony J.

    2010-01-01

    Spirituality and religion are not synonymous and, in fact, require not only different definitions but also appropriate vocabulary. A deeper discussion of the issues concerning spirituality ensues in several sections: 1) fundamental differences between spirituality and religion; 2) brain operations relative to transcendent states; 3) a definition…

  17. Spirituality in Music Education: Transcending Culture, Exploration III

    Science.gov (United States)

    Palmer, Anthony J.

    2010-01-01

    Spirituality and religion are not synonymous and, in fact, require not only different definitions but also appropriate vocabulary. A deeper discussion of the issues concerning spirituality ensues in several sections: 1) fundamental differences between spirituality and religion; 2) brain operations relative to transcendent states; 3) a definition…

  18. Pole distribution of PVI transcendents close to a critical point

    Science.gov (United States)

    Guzzetti, Davide

    2012-12-01

    The distribution of the poles of Painlevé VI transcendents associated to semi-simple Frobenius manifolds is determined close to a critical point. It is shown that the poles accumulate at the critical point, asymptotically along two rays. As an example, the Frobenius manifold given by the quantum cohomology of CP2 is considered. The general PVI is also considered.

  19. Nonequilibrium dynamics in chemical systems A brief account

    Science.gov (United States)

    Nicolis, G.; Baras, F.

    1985-12-01

    During the period of September 3 to 7, 1984 a symposium on “Nonequilibrium Dynamics in Chemical Systems” was organized by the Centre de Recherche Paul Pascal in Bordeaux, France. It was supported, primarily, by the French Centre National de la Recherche Scientifique and attended by about 90 participants from Australia, Belgium, Canada, Denmark, France, Germany, Hungary, Israël, Italy, Japan, The Netherlands, Poland, Tchekoslovakia, Spain, United Kingdom, United States and Zimbabwe. A list of topics and speakers is found in the table below. Two highly successful conferences centered on nonlinear phenomena in chemical systems far from equilibrium had already been organized by the Bordeaux group in the past. The first of them [1], held in September 1978, was dominated by the theme that nonequilibrium can act as a source of order. Sustained oscillations and bistability were the two principal phenomena studied from this point of view. Thanks to the systematic utilization of the continuous stirred tank reactor (CSTR) the study of open systems could finally be realized. Reliable state diagrams were thus produced, notably by the Bordeaux group, in which one could identify the transition points to new states. The Belousov-Zhabotinskii (BZ) reaction and its variants were the main vehicle on which these new ideas could be illustrated. The second Bordeaux conference [2], held in September 1981, was largely dominated by the major progress that had just marked two vital areas of this field: the discovery of new classes of chemical oscillators; and the invasion of chaotic dynamics in chemistry. These themes also dominated the first Gordon Conference on Chemical Oscillations held in New Hampshire in July 1982. In contrast to its two predecessors, the third Bordeaux conference held in September 1984 was not dominated by a single central theme. New questions were raised in situations in which until very recently things were considered to be perfectly clear. Simple,

  20. The Transcendence in Lucian Blaga’s Philosophical Thinking

    Directory of Open Access Journals (Sweden)

    Stelian Manolache

    2016-03-01

    Full Text Available On the occasion of the conference on Transcendence and Immanence - a topic buiding on the dialogue between philosophy and theology in the modern and post-modern time -, among the produced subjects, a discussion was held on the role played in respect with this dailogue by the inter-war famous philosophers, such as Lucian Blaga and Dumitru Stăniloaie. Below, we will present the issue of Transcendence according the the philosopher-poet Lucian Blaga’s vision; his vision is tructured into a Trilogy in his work: The Trilogy of Knowledge - The Dogmatic Aeon, The Luciferic Knowledge, The Transcendental Censorship - The Trilogy of the Culture - Horizon and Style; The Mioritic Space; The Genesis of the Metaphor and The Meaning of Culture - and The Trilogy of Values - Science and Creation; Magic Thinking and Religion; Art and Value. In these trilogies, the philosopher - poet elaborates, from an original metaphysical point of view, on the dimension of the knowledge of Transcendence - which he would define in in The Horizon of Mystery and Revelation. His vision will be addressed in a new theory of knowledge, which the philosopherpoet Lucian Blaga would distinguish as Paradisiac knowledge and Lucifer knowledge, within a new Metaphysics that would allow access to Transcendence and to the wonders beyond. Postulating the existence of certain faculties of Conscience, his Metaphysics would become, according to the Theory of Transcendence, a must for the human spirit; a proof for his approach would be the great philosophical systems of the world, from the antique to the modern.

  1. Determination of Reference Chemical Potential Using Molecular Dynamics Simulations

    Directory of Open Access Journals (Sweden)

    Krishnadeo Jatkar

    2010-01-01

    Full Text Available A new method implementing molecular dynamics (MD simulations for calculating the reference properties of simple gas hydrates has been proposed. The guest molecules affect interaction between adjacent water molecules distorting the hydrate lattice, which requires diverse values of reference properties for different gas hydrates. We performed simulations to validate the experimental data for determining Δ0, the chemical potential difference between water and theoretical empty cavity at the reference state, for structure II type gas hydrates. Simulations have also been used to observe the variation of the hydrate unit cell volume with temperature. All simulations were performed using TIP4P water molecules at the reference temperature and pressure conditions. The values were close to the experimental values obtained by the Lee-Holder model, considering lattice distortion.

  2. Theory of Transcendent unity of Religion

    Directory of Open Access Journals (Sweden)

    Hossein Ali Torkamany

    2015-09-01

    community". The Important result of The difference between vertical understanding from the horizontalis in the unity of religion. by the witness of nation of Islam - meaning the mediator between God and the Prophet of the People, the context of the unity and conflict resolution among the people to be provided. According toShiacommentators , the"moderate community" have minimal meaning and not maximal. Obtained on Shia traditions "moderate community" composed of some and not all Muslims, and some commentators have argued that the Quran is clear and apparent in dissatisfaction with some Muslims. According to the inward interpretation of Islam and "transcendent unity of religion", one religion over other religions have placed, it is the unity of religions. In general, the Quran, have especial comment on religions and none of the current theories do not fully explain the Quran's view. Quran calls into the word of God equally between religions, but this call to Islam is for all and no one is not who excluded from the invitation. and also the belief of the Prophet vertical, household, community center Shiites and people can be people through Bit interpreted not all Muslims claim Islam. Another important point is that the starting point should be first religion of anyone. At the end we can say: the theory of "transcendent unity of religions", with a focus on the true Islam and monotheistic religions version of the possibility of unity, has the following unique features: • the need to penetration in religionand religious invitation to unity of the religious path unique to each of them • struggle with exclusivismand requirement for progress of Muslims in unity • minimalistic interpretation of the moderate nation and the vertical understanding of witness. • The Holy Qur'an • Azizan, Mehdi, 2007, Pluralism In Islamic Thought , marifat, Vol:16, No:10(121, 13-25 • Asadi, Mohammad,2009, The religious pluralists unsuccessful in appealing to divine names and attributes ,Quran

  3. Consequences of an unstable chemical stratification on mantle dynamics

    Science.gov (United States)

    Plesa, Ana-Catalina; Tosi, Nicola; Breuer, Doris

    2013-04-01

    Early in the history of terrestrial planets, the fractional crystallization of primordial magma oceans may have led to the formation of large scale chemical heterogeneities. These may have been preserved over the entire planetary evolution as suggested for Mars by the isotopic analysis of the so-called SNC meteorites. The fractional crystallization of a magma ocean leads to a chemical stratification characterized by a progressive enrichment in heavy elements from the core-mantle boundary to the surface. This results in an unstable configuration that causes the overturn of the mantle and the subsequent formation of a stable chemical layering. Assuming scaling parameters appropriate for Mars, we first performed simulations of 2D thermo-chemical convection in Cartesian geometry with the numerical code YACC [1]. We investigated systems heated either solely from below or from within by varying systematically the buoyancy ratio B, which measures the relative importance of chemical to thermal buoyancy, and the mantle rheology, by considering systems with constant, strongly temperature-dependent and plastic viscosity. We ran a large set of simulations spanning a wide parameter space in order to understand the basic physics governing the magma ocean cumulate overturn and its consequence on mantle dynamics. Moreover, we derived scaling laws that relate the time over which chemical heterogeneities can be preserved (mixing time) and the critical yield stress (maximal yield stress that allows the lithosphere to undergo brittle failure) to the buoyancy ratio. We have found that the mixing time increases exponentially with B, while the critical yield stress shows a linear dependence. We investigated then Mars' early thermo-chemical evolution using the code GAIA in a 2D cylindrical geometry [2] and assuming a detailed magma ocean crystallization sequence as obtained from geochemical modeling [3]. We used an initial composition profile adapted from [3], accounted for an exothermic

  4. Dynamic behavior of chemical reactivity indices in density functional theory: A Bohn-Oppenheimer quantum molecular dynamics study

    Indian Academy of Sciences (India)

    Shubin Liu

    2005-09-01

    Dynamic behaviors of chemical concepts in density functional theory such as frontier orbitals (HOMO/LUMO), chemical potential, hardness, and electrophilicity index have been investigated in this work in the context of Bohn-Oppenheimer quantum molecular dynamics in association with molecular conformation changes. Exemplary molecular systems like CH$^{+}_{5}$ , Cl- (H2O)30 and Ca2+ (H2O)15 are studied at 300 K in the gas phase, demonstrating that HOMO is more dynamic than LUMO, chemical potential and hardness often fluctuate concurrently. It is argued that DFT concepts and indices may serve as a good framework to understand molecular conformation changes as well as other dynamic phenomena.

  5. From dynamic self-assembly to networked chemical systems.

    Science.gov (United States)

    Grzybowski, Bartosz A; Fitzner, Krzysztof; Paczesny, Jan; Granick, Steve

    2017-07-13

    Although dynamic self-assembly, DySA, is a relatively new area of research, the past decade has brought numerous demonstrations of how various types of components - on scales from (macro)molecular to macroscopic - can be arranged into ordered structures thriving in non-equilibrium, steady states. At the same time, none of these dynamic assemblies has so far proven practically relevant, prompting questions about the field's prospects and ultimate objectives. The main thesis of this Review is that formation of dynamic assemblies cannot be an end in itself - instead, we should think more ambitiously of using such assemblies as control elements (reconfigurable catalysts, nanomachines, etc.) of larger, networked systems directing sequences of chemical reactions or assembly tasks. Such networked systems would be inspired by biology but intended to operate in environments and conditions incompatible with living matter (e.g., in organic solvents, elevated temperatures, etc.). To realize this vision, we need to start considering not only the interactions mediating dynamic self-assembly of individual components, but also how components of different types could coexist and communicate within larger, multicomponent ensembles. Along these lines, the review starts with the discussion of the conceptual foundations of self-assembly in equilibrium and non-equilibrium regimes. It discusses key examples of interactions and phenomena that can provide the basis for various DySA modalities (e.g., those driven by light, magnetic fields, flows, etc.). It then focuses on the recent examples where organization of components in steady states is coupled to other processes taking place in the system (catalysis, formation of dynamic supramolecular materials, control of chirality, etc.). With these examples of functional DySA, we then look forward and consider conditions that must be fulfilled to allow components of multiple types to coexist, function, and communicate with one another within the

  6. Analysis of forward and inverse problems in chemical dynamics and spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Rabitz, H. [Princeton Univ., NJ (United States)

    1993-12-01

    The overall scope of this research concerns the development and application of forward and inverse analysis tools for problems in chemical dynamics and chemical kinetics. The chemical dynamics work is specifically associated with relating features in potential surfaces and resultant dynamical behavior. The analogous inverse research aims to provide stable algorithms for extracting potential surfaces from laboratory data. In the case of chemical kinetics, the focus is on the development of systematic means to reduce the complexity of chemical kinetic models. Recent progress in these directions is summarized below.

  7. On the study of nonlinear dynamics of complex chemical reaction systems

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    With ever-increasing attentions being paid to complex systems such as the life system, soft matter, and nano-systems, theoretical studies of non-equilibrium nonlinear problems involved in chemical dynamics are now of general interest. In this mini-review, we mainly give a brief introduction to some frontier topics in this field, namely, nonlinear state-state dynamics, nonlinear chemical dynamics on complex networks, and nonlinear dynamics in mesoscopic chemical reaction systems. Deep study of these topics will make great contribution to discovering new laws of chemical dynamics, to exploring new control methods of complex chemical processes, to figuring out the very roles of chemical processes in the life system, and to crosslinking the scientific study of chemistry, physics and biology.

  8. The quantum dynamics of electronically nonadiabatic chemical reactions

    Science.gov (United States)

    Truhlar, Donald G.

    1993-01-01

    Considerable progress was achieved on the quantum mechanical treatment of electronically nonadiabatic collisions involving energy transfer and chemical reaction in the collision of an electronically excited atom with a molecule. In the first step, a new diabatic representation for the coupled potential energy surfaces was created. A two-state diabatic representation was developed which was designed to realistically reproduce the two lowest adiabatic states of the valence bond model and also to have the following three desirable features: (1) it is more economical to evaluate; (2) it is more portable; and (3) all spline fits are replaced by analytic functions. The new representation consists of a set of two coupled diabatic potential energy surfaces plus a coupling surface. It is suitable for dynamics calculations on both the electronic quenching and reaction processes in collisions of Na(3p2p) with H2. The new two-state representation was obtained by a three-step process from a modified eight-state diatomics-in-molecules (DIM) representation of Blais. The second step required the development of new dynamical methods. A formalism was developed for treating reactions with very general basis functions including electronically excited states. Our formalism is based on the generalized Newton, scattered wave, and outgoing wave variational principles that were used previously for reactive collisions on a single potential energy surface, and it incorporates three new features: (1) the basis functions include electronic degrees of freedom, as required to treat reactions involving electronic excitation and two or more coupled potential energy surfaces; (2) the primitive electronic basis is assumed to be diabatic, and it is not assumed that it diagonalizes the electronic Hamiltonian even asymptotically; and (3) contracted basis functions for vibrational-rotational-orbital degrees of freedom are included in a very general way, similar to previous prescriptions for locally

  9. Newly-graduated midwives transcending barriers: a grounded theory study.

    Science.gov (United States)

    Barry, Michele J; Hauck, Yvonne L; O'Donoghue, Thomas; Clarke, Simon

    2013-12-01

    Midwifery has developed its own philosophy to formalise its unique identity as a profession. Newly-graduated midwives are taught, and ideally embrace, this philosophy during their education. However, embarking in their career within a predominantly institutionalised and the medically focused health-care model may challenge this application. The research question guiding this study was as follows: 'How do newly graduated midwives deal with applying the philosophy of midwifery in their first six months of practice?' The aim was to generate a grounded theory around this social process. This Western Australian grounded theory study is conceptualised within the social theory of symbolic interactionism. Data were collected by means of in-depth, semi-structured interviews with 11 recent midwifery graduates. Participant and interviewer's journals provided supplementary data. The 'constant comparison' approach was used for data analysis. The substantive theory of transcending barriers was generated. Three stages in transcending barriers were identified: Addressing personal attributes, Understanding the 'bigger picture', and finally, 'Evaluating, planning and acting' to provide woman-centred care. An overview of these three stages provides the focus of this article. The theory of transcending barriers provides a new perspective on how newly-graduated midwives deal with applying the philosophy of midwifery in their first six months of practice. A number of implications for pre and post registration midwifery education and policy development are suggested, as well as recommendations for future research. Copyright © 2013 Elsevier Ltd. All rights reserved.

  10. Dynamic Adsorptive Removal of Toxic Chemicals for Purification of Water

    Directory of Open Access Journals (Sweden)

    Amit Saxena

    2005-04-01

    Full Text Available To determine the efficiency of carbon column for the removal of toxic chemicals from water, the adsorption of phenol in concentration range from 0.600 glt to 1.475 gll was studied on activecarbon of 80 CTC grade, 12 X 30 BSS particle size, 1280 m2/g surface area, and of coconut shell origin, under dynamic conditions at space velocity from 0.318 min-' to 4.24 min-' at 25 'C. The carbon column of 100 cm length and 2 cm diameter was found to be removing phenol from the aqueous solution of concentration 1.475 gll up to 84 min at 0.678 min-' space velocity at 5.0 ppm phenol breakthrough concentration. However, no phenol was observed in carbon-treated water after 80 min. The service life of carbon column (100 cm lengthX25 cm diameter was assessed through the water purification system developed at the Defence Laboratory, Jodhpur and was determined to be 4.095 days with twoas factor of safety for 10 ppm initial concentration of phenol at 0.678 min-' space velocity (corresponding to water flow rate. Effects of carbon bed length, water flow rate, and the phenol concentration were also studied.

  11. Spatially organized dynamical states in chemical oscillator networks: synchronization, dynamical differentiation, and chimera patterns.

    Directory of Open Access Journals (Sweden)

    Mahesh Wickramasinghe

    Full Text Available Dynamical processes in many engineered and living systems take place on complex networks of discrete dynamical units. We present laboratory experiments with a networked chemical system of nickel electrodissolution in which synchronization patterns are recorded in systems with smooth periodic, relaxation periodic, and chaotic oscillators organized in networks composed of up to twenty dynamical units and 140 connections. The reaction system formed domains of synchronization patterns that are strongly affected by the architecture of the network. Spatially organized partial synchronization could be observed either due to densely connected network nodes or through the 'chimera' symmetry breaking mechanism. Relaxation periodic and chaotic oscillators formed structures by dynamical differentiation. We have identified effects of network structure on pattern selection (through permutation symmetry and coupling directness and on formation of hierarchical and 'fuzzy' clusters. With chaotic oscillators we provide experimental evidence that critical coupling strengths at which transition to identical synchronization occurs can be interpreted by experiments with a pair of oscillators and analysis of the eigenvalues of the Laplacian connectivity matrix. The experiments thus provide an insight into the extent of the impact of the architecture of a network on self-organized synchronization patterns.

  12. Exploitation of Chemical Signaling by Parasitoids: Impact on Host Population Dynamics

    NARCIS (Netherlands)

    Lof, M.E.; Gee, de M.; Dicke, M.; Gort, G.; Hemerik, L.

    2013-01-01

    Chemical information mediates species interactions in a wide range of organisms. Yet, the effect of chemical information on population dynamics is rarely addressed. We designed a spatio-temporal parasitoid—host model to investigate the population dynamics when both the insect host and the parasitic

  13. Molecular Dynamics Simulations of Chemical Reactions for Use in Education

    Science.gov (United States)

    Qian Xie; Tinker, Robert

    2006-01-01

    One of the simulation engines of an open-source program called the Molecular Workbench, which can simulate thermodynamics of chemical reactions, is described. This type of real-time, interactive simulation and visualization of chemical reactions at the atomic scale could help students understand the connections between chemical reaction equations…

  14. Molecular Dynamics Simulations of Chemical Reactions for Use in Education

    Science.gov (United States)

    Qian Xie; Tinker, Robert

    2006-01-01

    One of the simulation engines of an open-source program called the Molecular Workbench, which can simulate thermodynamics of chemical reactions, is described. This type of real-time, interactive simulation and visualization of chemical reactions at the atomic scale could help students understand the connections between chemical reaction equations…

  15. Chemical reaction dynamics of PeCB and TCDD decomposition: A tight-binding quantum chemical molecular dynamics study with first-principles parameterization

    Science.gov (United States)

    Suzuki, Ai; Selvam, Parasuraman; Kusagaya, Tomonori; Takami, Seiichi; Kubo, Momoji; Imamura, Akira; Miyamoto, Akira

    The decomposition reaction dynamics of 2,3,4,4',5-penta-chlorinated biphenyl (2,3,4,4',5-PeCB), 3,3',4,4',5-penta-chlorinated biphenyl (3,3',4,4',5-PeCB), and 2,3,7,8-tetra-chlorinated dibenzo-p-dioxin (2,3,7,8-TCDD) was clarified for the first time at atomic and electronic levels, using our novel tight-binding quantum chemical molecular dynamics method with first-principles parameterization. The calculation speed of our new method is over 5000 times faster than that of the conventional first-principles molecular dynamics method. We confirmed that the structure, energy, and electronic states of the above molecules calculated by our new method are quantitatively consistent with those by first-principles calculations. After the confirmation of our methodology, we investigated the decomposition reaction dynamics of the above molecules and the calculated dynamic behaviors indicate that the oxidation of the 2,3,4,4',5-PeCB, 3,3',4,4',5-PeCB, and 2,3,7,8-TCDD proceeds through an epoxide intermediate, which is in good agreement with the previous experimental reports and consistent with our static density functional theory calculations. These results proved that our new tight-binding quantum chemical molecular dynamics method with first-principles parameterization is an effective tool to clarify the chemical reaction dynamics at reaction temperatures.

  16. Vacuum Ultraviolet Laser Probe of Chemical Dynamics of Aerospace Relevance

    Science.gov (United States)

    2012-09-12

    valuable for modeling aerospace environments using the Direct Simulation Monte Carlo and Particles in Cell methods. Environments of interest to the...School of Chemical Biology and Biotechnology”, Shenzhen , China, Nov. 21, 2010. 29. C. Y. Ng, “The Role of Basic (Chemical) Research in Modern

  17. Correlation between dynamic wetting behavior and chemical components of thermally modified wood

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Wang; Zhu, Yuan; Cao, Jinzhen, E-mail: caoj@bjfu.edu.cn; Sun, Wenjing

    2015-01-01

    Highlights: • We studied the dynamic wetting behavior of thermally modified wood by wetting models. • We found lower wetting speed of water droplets on thermally modified wood surface. • Dynamic wetting behavior and surface chemical components show a strong correlation. - Abstract: In order to investigate the dynamic wetting behavior of thermally modified wood, Cathay poplar (Populus cathayana Rehd.) and Scots pine (Pinus sylvestris L.) samples were thermally modified in an oven at 160, 180, 200, 220 or 240 °C for 4 h in this study. The dynamic contact angles and droplet volumes of water droplets on modified and unmodified wood surfaces were measured by sessile drop method, and their changing rates (expression index: K value and wetting slope) calculated by wetting models were illustrated for mapping the dynamic wetting process. The surface chemical components were also measured by X-ray photoelectron spectroscopy analysis (XPS), thus the relationship between dynamic wetting behavior and chemical components of thermally modified wood were determined. The results indicated that thermal modification was capable of decreasing the dynamic wettability of wood, expressed in lowing spread and penetration speed of water droplets on wood surfaces. This change was more obvious with the increased heating temperature. The K values varied linearly with the chemical components parameter (mass loss, O/C ratio, and C{sub 1}/C{sub 2} ratio), indicating a strong correlation between dynamic wetting behavior and chemical components of thermally modified wood.

  18. Group calls for space policies to transcend politics

    Science.gov (United States)

    Showstack, Randy

    2012-06-01

    At a 22 May briefing, the American Institute of Aeronautics and Astronautics (AIAA) called on Congress to “establish space exploration policy goals which transcend partisan political differences.” AIAA president and former NASA administrator Michael Griffin said the “goal of establishing human capability to b e a space-faring species is not a short-term goal,” nor is it a goal that belongs to only one political party. “We will not reach long-term goals without a stable, coherent, sensible plan that transcends elections and leaders,” said Griffin, who has provided advice to Republican U.S. presidential candidate Mitt Romney. Griffin pointed to NASA's 2008 authorization as providing the kind of vision needed for NASA. The act called for human return to the Moon and preparation for the capability for permanent bases on the Moon, among other things, he said. “That's the kind of thing that we need. All of the goals espoused by the 2008 act were long-term, generational, strategic in scope,” Griffin said, adding that the act, which had bipartisan support, demonstrated “the kind of societal support, rather than political support, that I believe our space program deserves.”

  19. Chemical Kinetics, Heat Transfer, and Sensor Dynamics Revisited in a Simple Experiment

    Science.gov (United States)

    Sad, Maria E.; Sad, Mario R.; Castro, Alberto A.; Garetto, Teresita F.

    2008-01-01

    A simple experiment about thermal effects in chemical reactors is described, which can be used to illustrate chemical reactor models, the determination and validation of their parameters, and some simple principles of heat transfer and sensor dynamics. It is based in the exothermic reaction between aqueous solutions of sodium thiosulfate and…

  20. Chemical Kinetics, Heat Transfer, and Sensor Dynamics Revisited in a Simple Experiment

    Science.gov (United States)

    Sad, Maria E.; Sad, Mario R.; Castro, Alberto A.; Garetto, Teresita F.

    2008-01-01

    A simple experiment about thermal effects in chemical reactors is described, which can be used to illustrate chemical reactor models, the determination and validation of their parameters, and some simple principles of heat transfer and sensor dynamics. It is based in the exothermic reaction between aqueous solutions of sodium thiosulfate and…

  1. Crossed Molecular Beam Studies and Dynamics of Decomposition of Chemically Activated Radicals

    Science.gov (United States)

    Lee, Y. T.

    1973-09-01

    The power of the crossed molecular beams method in the investigation of the dynamics of chemical reactions lies mainly in the direct observation of the consequences of single collisions of well controlled reactant molecules. The primary experimental observations which provide information on reaction dynamics are the measurements of angular and velocity distributions of reaction products.

  2. Design of multi-phase dynamic chemical networks

    Science.gov (United States)

    Chen, Chenrui; Tan, Junjun; Hsieh, Ming-Chien; Pan, Ting; Goodwin, Jay T.; Mehta, Anil K.; Grover, Martha A.; Lynn, David G.

    2017-08-01

    Template-directed polymerization reactions enable the accurate storage and processing of nature's biopolymer information. This mutualistic relationship of nucleic acids and proteins, a network known as life's central dogma, is now marvellously complex, and the progressive steps necessary for creating the initial sequence and chain-length-specific polymer templates are lost to time. Here we design and construct dynamic polymerization networks that exploit metastable prion cross-β phases. Mixed-phase environments have been used for constructing synthetic polymers, but these dynamic phases emerge naturally from the growing peptide oligomers and create environments suitable both to nucleate assembly and select for ordered templates. The resulting templates direct the amplification of a phase containing only chain-length-specific peptide-like oligomers. Such multi-phase biopolymer dynamics reveal pathways for the emergence, self-selection and amplification of chain-length- and possibly sequence-specific biopolymers.

  3. Vulnerability to alcohol consumption, spiritual transcendence and psychosocial well-being: test of a theory

    Directory of Open Access Journals (Sweden)

    Luz Patricia Díaz Heredia

    2016-01-01

    Full Text Available Abstract Objective: to demonstrate the relations among vulnerability, self-transcendence and well-being in the young adult population and the effect of each of these variables on the adoption of low-risk consumption conducts. Method: quantitative and cross-sectional correlation study using structural equations analysis to test the relation among the variables. Results: an inverse relation was evidenced between vulnerability to alcohol consumption and spiritual transcendence (β-0.123, p 0.025 and a direct positive relation between spiritual transcendence and psychosocial well-being (β 0.482, p 0.000. Conclusions: the relations among the variables spiritual transcendence, vulnerability to alcohol consumption and psychosocial well-being, based on Reed's Theory, are confirmed in the population group of young college students, concluding that psychosocial well-being can be achieved when spiritual transcendence is enhanced, as the vulnerability to alcohol consumption drops.

  4. Advances in chemical physics dynamical processes in condensed matter

    CERN Document Server

    Evans, Myron W

    2009-01-01

    Transport Properties and Soliton Models for Polyacetylene (M. Andretta, et al.). Development and Application of the Theory of Brownian Motion (W. Coffey). The Fading of Memory During the Regression of Structural Fluctuations (L. Dissado, et al.). Cooperative Molecular Behavior and Field Effects on Liquids: Experimental Considerations (G. Evans). A Review and Computer Simulation of the Molecular Dynamics of a Series of Specific Molecular Liquids (M. Evans and G. Evans). Recent Advances in Molecular-Dynamics Computer Simulation (D. Fincham and D. Heyes). Nonadiabatic Scattering Probl

  5. Transposing, Transforming and Transcending Tradition in Creative Digital Media

    DEFF Research Database (Denmark)

    Prager, Phillip; Thomas, Maureen; Selsjord, Marianne

    2015-01-01

    and storytelling arts combine to create rich, complex, and engaging moving-image based artworks with wide appeal. It examines how dramatist and interactive media artist Maureen Thomas and 3D media artist and conservator Marianne Selsjord deploy creative digital technologies to transpose, transform, and transcend...... of the aspirations and approaches of 20th-century avant-garde artists, revealing these as a potent source of conceptual riches for the digital media creators of today and tomorrow.......How can digital media technologies, contemporary theories of creativity, and tradition combine to develop the aesthetics of computer-based art today and in the future? Through contextualised case-studies, this chapter investigates how games, information technologies, and traditional visual...

  6. Narcissistic biographies--third age self-transcendence abilities.

    Science.gov (United States)

    Nirestean, Aurel; Lukacs, Emese; Cimpan, Dana; Nirestean, Tudor

    2014-02-01

    Narcissistic traits interfere in the process of self-determination and the individual motivational strategies of human beings. The grandiose and vulnerable narcissistic personality subtypes have difficulties in their education, interpersonal relationships and quality of life. The latter is also affected by ageing, whose attributes influence, above all, one's self-esteem, especially in women. Though very fearful of suffering and death, narcissists have a powerful desire to overcome them by cultivating their grandiosity, especially through the mystical and paranormal experiences they relate. The spiritual means of transcending one's self, including the components of magical thinking, can prevent the destruction of self-esteem in narcissists in their third-age. Copyright © 2014 John Wiley & Sons, Ltd.

  7. Transposing, Transforming and Transcending Tradition in Creative Digital Media

    DEFF Research Database (Denmark)

    Prager, Phillip; Thomas, Maureen; Selsjord, Marianne

    2015-01-01

    How can digital media technologies, contemporary theories of creativity, and tradition combine to develop the aesthetics of computer-based art today and in the future? Through contextualised case-studies, this chapter investigates how games, information technologies, and traditional visual...... and storytelling arts combine to create rich, complex, and engaging moving-image based artworks with wide appeal. It examines how dramatist and interactive media artist Maureen Thomas and 3D media artist and conservator Marianne Selsjord deploy creative digital technologies to transpose, transform, and transcend...... of the aspirations and approaches of 20th-century avant-garde artists, revealing these as a potent source of conceptual riches for the digital media creators of today and tomorrow....

  8. Agent-Based Chemical Plume Tracing Using Fluid Dynamics

    Science.gov (United States)

    Zarzhitsky, Dimitri; Spears, Diana; Thayer, David; Spears, William

    2004-01-01

    This paper presents a rigorous evaluation of a novel, distributed chemical plume tracing algorithm. The algorithm is a combination of the best aspects of the two most popular predecessors for this task. Furthermore, it is based on solid, formal principles from the field of fluid mechanics. The algorithm is applied by a network of mobile sensing agents (e.g., robots or micro-air vehicles) that sense the ambient fluid velocity and chemical concentration, and calculate derivatives. The algorithm drives the robotic network to the source of the toxic plume, where measures can be taken to disable the source emitter. This work is part of a much larger effort in research and development of a physics-based approach to developing networks of mobile sensing agents for monitoring, tracking, reporting and responding to hazardous conditions.

  9. RPMDrate: Bimolecular chemical reaction rates from ring polymer molecular dynamics

    KAUST Repository

    Suleimanov, Yu.V.

    2013-03-01

    We present RPMDrate, a computer program for the calculation of gas phase bimolecular reaction rate coefficients using the ring polymer molecular dynamics (RPMD) method. The RPMD rate coefficient is calculated using the Bennett-Chandler method as a product of a static (centroid density quantum transition state theory (QTST) rate) and a dynamic (ring polymer transmission coefficient) factor. The computational procedure is general and can be used to treat bimolecular polyatomic reactions of any complexity in their full dimensionality. The program has been tested for the H+H2, H+CH 4, OH+CH4 and H+C2H6 reactions. © 2012 Elsevier B.V. All rights reserved.

  10. Effect of Coriolis coupling in chemical reaction dynamics.

    Science.gov (United States)

    Chu, Tian-Shu; Han, Ke-Li

    2008-05-14

    It is essential to evaluate the role of Coriolis coupling effect in molecular reaction dynamics. Here we consider Coriolis coupling effect in quantum reactive scattering calculations in the context of both adiabaticity and nonadiabaticity, with particular emphasis on examining the role of Coriolis coupling effect in reaction dynamics of triatomic molecular systems. We present the results of our own calculations by the time-dependent quantum wave packet approach for H + D2 and F(2P3/2,2P1/2) + H2 as well as for the ion-molecule collisions of He + H2 +, D(-) + H2, H(-) + D2, and D+ + H2, after reviewing in detail other related research efforts on this issue.

  11. Wide Dynamic Range CMOS Potentiostat for Amperometric Chemical Sensor

    Directory of Open Access Journals (Sweden)

    Wei-Song Wang

    2010-03-01

    Full Text Available Presented is a single-ended potentiostat topology with a new interface connection between sensor electrodes and potentiostat circuit to avoid deviation of cell voltage and linearly convert the cell current into voltage signal. Additionally, due to the increased harmonic distortion quantity when detecting low-level sensor current, the performance of potentiostat linearity which causes the detectable current and dynamic range to be limited is relatively decreased. Thus, to alleviate these irregularities, a fully-differential potentiostat is designed with a wide output voltage swing compared to single-ended potentiostat. Two proposed potentiostats were implemented using TSMC 0.18-μm CMOS process for biomedical application. Measurement results show that the fully differential potentiostat performs relatively better in terms of linearity when measuring current from 500 ºpA to 10 uA. Besides, the dynamic range value can reach a value of 86 dB.

  12. Wide Dynamic Range CMOS Potentiostat for Amperometric Chemical Sensor

    OpenAIRE

    Wei-Song Wang; Wei-Ting Kuo; Hong-Yi Huang; Ching-Hsing Luo

    2010-01-01

    Presented is a single-ended potentiostat topology with a new interface connection between sensor electrodes and potentiostat circuit to avoid deviation of cell voltage and linearly convert the cell current into voltage signal. Additionally, due to the increased harmonic distortion quantity when detecting low-level sensor current, the performance of potentiostat linearity which causes the detectable current and dynamic range to be limited is relatively decreased. Thus, to alleviate these irreg...

  13. Time-resolved imaging of purely valence-electron dynamics during a chemical reaction

    DEFF Research Database (Denmark)

    Hockett, Paul; Bisgaard, Christer Z.; Clarkin, Owen J.

    2011-01-01

    Chemical reactions are manifestations of the dynamics of molecular valence electrons and their couplings to atomic motions. Emerging methods in attosecond science can probe purely electronic dynamics in atomic and molecular systems(1-6). By contrast, time-resolved structural-dynamics methods......,17): in both cases, this sensitivity derives from the ionization-matrix element(18,19). Here we demonstrate a time-resolved molecular-frame photoelectron-angular-distribution (TRMFPAD) method for imaging the purely valence-electron dynamics during a chemical reaction. Specifically, the TRMFPADs measured during...... the non-adiabatic photodissociation of carbon disulphide demonstrate how the purely electronic rearrangements of the valence electrons can be projected from inherently coupled electronic-vibrational dynamics. Combined with ongoing efforts in molecular frame alignment(20) and orientation(21,22), TRMFPADs...

  14. Dynamics of the chemical composition of rainwater throughout Hurricane Irene

    Directory of Open Access Journals (Sweden)

    K. M. Mullaugh

    2013-03-01

    Full Text Available Sequential sampling of rainwater from Hurricane Irene was carried out in Wilmington, NC, USA on 26 and 27 August 2011. Eleven samples were analyzed for pH, major ions (Cl−, NO3−, SO42−, Na+, K+, Mg2+, Ca2+, NH4+, dissolved organic carbon (DOC and hydrogen peroxide (H2O2. Hurricane Irene contributed 16% of the total rainwater and 18% of the total chloride wet deposition received in Wilmington NC during all of 2011. This work highlights the main physical factors influencing the chemical composition of tropical storm rainwater: wind speed, wind direction, back trajectory and vertical mixing, time of day and total rain volume. Samples collected early in the storm, when winds blew out of the east, contained dissolved components indicative of marine sources (salts from sea spray and low DOC. The sea-salt components in the samples had two maxima in concentration during the storm the first of which occurred before the volume of rain had sufficiently washed out sea salt from the atmosphere and the second when back trajectories showed large volumes of marine surface air were lifted. As the storm progressed and winds shifted to a westerly direction, the chemical composition of the rainwater became characteristic of terrestrial storms (high DOC and NH4+ and low sea salt. This work demonstrates that tropical storms are not only responsible for significant wet deposition of marine components to land, but terrestrial components can also become entrained in rainwater, which can then be delivered to coastal waters via wet deposition. This study also underscores why analysis of one composite sample can lead to an incomplete interpretation of the factors that influence the chemically divergent analytes in rainwater during extreme weather events.

  15. Correlation between dynamic wetting behavior and chemical components of thermally modified wood

    Science.gov (United States)

    Wang, Wang; Zhu, Yuan; Cao, Jinzhen; Sun, Wenjing

    2015-01-01

    In order to investigate the dynamic wetting behavior of thermally modified wood, Cathay poplar (Populus cathayana Rehd.) and Scots pine (Pinus sylvestris L.) samples were thermally modified in an oven at 160, 180, 200, 220 or 240 °C for 4 h in this study. The dynamic contact angles and droplet volumes of water droplets on modified and unmodified wood surfaces were measured by sessile drop method, and their changing rates (expression index: K value and wetting slope) calculated by wetting models were illustrated for mapping the dynamic wetting process. The surface chemical components were also measured by X-ray photoelectron spectroscopy analysis (XPS), thus the relationship between dynamic wetting behavior and chemical components of thermally modified wood were determined. The results indicated that thermal modification was capable of decreasing the dynamic wettability of wood, expressed in lowing spread and penetration speed of water droplets on wood surfaces. This change was more obvious with the increased heating temperature. The K values varied linearly with the chemical components parameter (mass loss, O/C ratio, and C1/C2 ratio), indicating a strong correlation between dynamic wetting behavior and chemical components of thermally modified wood.

  16. Correlation of chemical shifts predicted by molecular dynamics simulations for partially disordered proteins

    Energy Technology Data Exchange (ETDEWEB)

    Karp, Jerome M.; Erylimaz, Ertan; Cowburn, David, E-mail: cowburn@cowburnlab.org, E-mail: David.cowburn@einstein.yu.edu [Albert Einstein College of Medicine of Yeshiva University, Department of Biochemistry (United States)

    2015-01-15

    There has been a longstanding interest in being able to accurately predict NMR chemical shifts from structural data. Recent studies have focused on using molecular dynamics (MD) simulation data as input for improved prediction. Here we examine the accuracy of chemical shift prediction for intein systems, which have regions of intrinsic disorder. We find that using MD simulation data as input for chemical shift prediction does not consistently improve prediction accuracy over use of a static X-ray crystal structure. This appears to result from the complex conformational ensemble of the disordered protein segments. We show that using accelerated molecular dynamics (aMD) simulations improves chemical shift prediction, suggesting that methods which better sample the conformational ensemble like aMD are more appropriate tools for use in chemical shift prediction for proteins with disordered regions. Moreover, our study suggests that data accurately reflecting protein dynamics must be used as input for chemical shift prediction in order to correctly predict chemical shifts in systems with disorder.

  17. The effect of peer support group on self-transcendence in patients undergoing haemodialysis

    Directory of Open Access Journals (Sweden)

    Maryam Jadid Milani

    2017-03-01

    Full Text Available Introduction: Self-transcendence helps patients undergoing haemodialysis to organize the variety of challenges caused by the disease in order to make them feel well. This study  was   conducted  to determine the effect of counterpart group on improving self-transcendence level in patients undergoing haemodialysis. Materials and Methods: This clinical trial was conducted with two groups of intervention and control, with 55 patients undergoing hemodialysis. The samples were divided in 2 groups of intervention and control through block randomization. Two-hour counterpart group sessions were held for eight weeks for intervention group. The session's topics were based on the patients’ needs and interests. Research tools were questionnaire, demographic information and "Reed’s Self-Transcendence Scale (STS". The descriptive and inferential statistics were used for data analysis using the SPSS v18. Results: There was a significant difference between self-transcendence scores in two groups of intervention and control (P<0.05. A significant increase in the level of self-transcendence in both groups was seen at the end of the study compared to basal status (P<0.05. Conclusions: According to the study results, attending the counterpart groups improved  self-transcendence in patients undergoing haemodialysis. The results can be used in nursing education and management. Training Self-transcendence evaluation is recommended for other chronic diseases with the emphasize on participating in counterpart groups for assessing its efficiency.

  18. Transimmanence and the Im/possible Relationship between Eschatology and Transcendence

    Directory of Open Access Journals (Sweden)

    Anné Hendrik Verhoef

    2016-11-01

    Full Text Available Although we live in a post-metaphysical age, there is a renewed interest in transcendence, especially at the intersection of philosophy, religion, and theology. There are several reasons for this: among others, the important link that the future (eschatology has with the unknown or that which lies beyond (transcendence. In this article, this relation between eschatology and transcendence is explored by analysing different concepts of transcendence and their possible relations to the future. Jacques Derrida and Catharine Malabou’s concepts of the future are used to shed light on the link between eschatology and transcendence as “impossible”. Secondly, Jean-Luc Nancy’s concept of transimmanence is introduced, in an attempt to find such a possible link. A reconceptualisation of transcendence as transimmanence and a reconceptualisation of the future of eschatology as something “outside within”, facilitate a link between these terms, but the original or general meanings of these terms then become impossible. This outcome urges a rethinking of the meaning and role of transcendence, eschatology, and the future in our post-metaphysical age.

  19. Dynamical resonance in F+H2 chemical reaction and rotational excitation effect

    Institute of Scientific and Technical Information of China (English)

    YANG XueMing; XIE DaiQian; ZHANG DongHui

    2007-01-01

    Reaction resonance is a frontier topic in chemical dynamics research, and it is also essential to the understanding of mechanisms of elementary chemical reactions. This short article describes an important development in the frontier of research. Experimental evidence of reaction resonance has been detected in a full quantum state resolved reactive scattering study of the F+H2 reaction. Highly accurate full quantum scattering theoretical modeling shows that the reaction resonance is caused by two Feshbach resonance states. Further studies show that quantum interference is present between the two resonance states for the forward scattering product. This study is a significant step forward in our understanding of chemical reaction resonance in the benchmark F+H2 system. Further experimental studies on the effect of H2 rotational excitation on dynamical resonance have been carried out. Dynamical resonance in the F+H2 (j = 1) reaction has also been observed.

  20. Dynamical and chemical evolution of the thin disc

    Science.gov (United States)

    Just, A.; Rybizki, J.

    2016-09-01

    Our detailed analytic local disc model (JJ-model) quantifies the interrelation between kinematic properties (e.g. velocity dispersions and asymmetric drift), spatial parameters (scale-lengths and vertical density profiles), and properties of stellar sub-populations (age and abundance distributions). Any consistent radial extension of the disc evolution model should predict specific features in the different distribution functions and in their correlations. Large spectroscopic surveys (SEGUE, RAVE, APOGEE, Gaia-ESO) allow significant constraints on the long-term evolution of the thin disc. We discuss the qualitative difference of correlations (like the α-enhancement as function of metallicity) and distribution functions (e.g. in [Mg/H] or [Fe/H]) for the construction of a disc model. In the framework of the JJ-model we build a local chemical enrichment model and show that significant vertical gradients for main sequence and red clump stars are expected in the thin disc. A Jeans analysis of the asymmetric drift provides a link to the radial structure of the disc. The derived metallicity-dependent radial scale-lengths can be combined in the future with the abundance distributions at different Galactocentric distances to construct full disc models. We expect to be able to constrain possible scenarios of inside-out growth of the thin disc and to characterise those populations, which require significant radial migration.

  1. Dynamical and chemical evolution of the thin disc

    CERN Document Server

    Just, Andreas

    2015-01-01

    Our detailed analytic local disc model (JJ-model) quantifies the interrelation between kinematic properties (e.g. velocity dispersions and asymmetric drift), spatial parameters (scale-lengths and vertical density profiles), and properties of stellar sub-populations (age and abundance distributions). Any consistent radial extension of the disc evolution model should predict specific features in the different distribution functions and in their correlations. Large spectroscopic surveys (SEGUE, RAVE, APOGEE, Gaia-ESO) allow significant constraints on the long-term evolution of the thin disc. We discuss the qualitative difference of correlations (like the alpha-enhancement as function of metallicity) and distribution functions (e.g. in [Mg/H] or [Fe/H]) for the construction of a disc model. In the framework of the JJ-model we build a local chemical enrichment model and show that significant vertical gradients for main sequence and red clump stars are expected in the thin disc. A Jeans analysis of the asymmetric d...

  2. Transcender com a natureza: a espiritualidade para os idosos

    Directory of Open Access Journals (Sweden)

    Rosimere Ferreira Santana

    2005-08-01

    Full Text Available Considerando que as pessoas possuem uma dimensão imaginativa sobre seu modo de viver, apresentamos o problema: Qual é o imaginário dos idosos sobre envelhecimento? Nosso objetivo: descrever a poética dos idosos sobre o envelhecer identificando possibilidades de inovação na prática de enfermagem gerontológica desde a compreensão do seu imaginário. Selecionamos o método sociopoético e seu dispositivo analítico - grupo pesquisador (GP, para aplicar a técnica de pesquisa Vivência dos Lugares Geomíticos, considerando a questão norteadora: “se o envelhecer fosse um lugar geomítico, como seria?”. A investigação realizou-se na UnATI / UERJ, de 2003 a 2004, analisando-se a produção de dados dos 28 idosos componentes do GP, junto à pesquisadora, mediante o estudo sociopoético denominado infantil / surrealista. Entre os resultados, destacam-se os seguintes lugares associados aos temas: Arco-Íris, Caminho, Limiar / Transcender com a natureza; Ponte, Limiar, Arco-Íris / Espiritualidade; Caminho, Limiar e Arco-Íris / Alegria interior. Na experimentação/ interpretação dos resultados, destacam-se as categorias: Transcender com a natureza - demonstra a busca dos idosos pela sua integração ao cosmo, seu inconsciente tomado de espiritualidade; A busca da alegria começa em nosso interior - quando estamos próximos da velhice, inicia-se o ciclo cósmico, um momento que propicia maior discernimento / tomada de consciência. Concluímos que o imaginário dos idosos revela o desejo de encontrar-se com a natureza, integrando-se ao cosmo e não à morte da estrutura física, pois que sentido faria a vida se só tivéssemos a morte? Para inovar a enfermagem em gerontologia, devemos promover entre as pessoas a percepção da inter-relação de todas as coisas, pois o GP descobriu que o contato com a natureza revela a necessidade de interação porque ela é vida e, como nos seres humanos, a natureza é energia restauradora.

  3. Dynamic range in small-world networks of Hodgkin-Huxley neurons with chemical synapses

    Science.gov (United States)

    Batista, C. A. S.; Viana, R. L.; Lopes, S. R.; Batista, A. M.

    2014-09-01

    According to Stevens' law the relationship between stimulus and response is a power-law within an interval called the dynamic range. The dynamic range of sensory organs is found to be larger than that of a single neuron, suggesting that the network structure plays a key role in the behavior of both the scaling exponent and the dynamic range of neuron assemblies. In order to verify computationally the relationships between stimulus and response for spiking neurons, we investigate small-world networks of neurons described by the Hodgkin-Huxley equations connected by chemical synapses. We found that the dynamic range increases with the network size, suggesting that the enhancement of the dynamic range observed in sensory organs, with respect to single neurons, is an emergent property of complex network dynamics.

  4. Single-molecule chemical reaction reveals molecular reaction kinetics and dynamics.

    Science.gov (United States)

    Zhang, Yuwei; Song, Ping; Fu, Qiang; Ruan, Mingbo; Xu, Weilin

    2014-06-25

    Understanding the microscopic elementary process of chemical reactions, especially in condensed phase, is highly desirable for improvement of efficiencies in industrial chemical processes. Here we show an approach to gaining new insights into elementary reactions in condensed phase by combining quantum chemical calculations with a single-molecule analysis. Elementary chemical reactions in liquid-phase, revealed from quantum chemical calculations, are studied by tracking the fluorescence of single dye molecules undergoing a reversible redox process. Statistical analyses of single-molecule trajectories reveal molecular reaction kinetics and dynamics of elementary reactions. The reactivity dynamic fluctuations of single molecules are evidenced and probably arise from either or both of the low-frequency approach of the molecule to the internal surface of the SiO2 nanosphere or the molecule diffusion-induced memory effect. This new approach could be applied to other chemical reactions in liquid phase to gain more insight into their molecular reaction kinetics and the dynamics of elementary steps.

  5. A Grid-Based Cyber Infrastructure for High Performance Chemical Dynamics Simulations

    Directory of Open Access Journals (Sweden)

    Khadka Prashant

    2008-10-01

    Full Text Available Chemical dynamics simulation is an effective means to study atomic level motions of molecules, collections of molecules, liquids, surfaces, interfaces of materials, and chemical reactions. To make chemical dynamics simulations globally accessible to a broad range of users, recently a cyber infrastructure was developed that provides an online portal to VENUS, a popular chemical dynamics simulation program package, to allow people to submit simulation jobs that will be executed on the web server machine. In this paper, we report new developments of the cyber infrastructure for the improvement of its quality of service by dispatching the submitted simulations jobs from the web server machine onto a cluster of workstations for execution, and by adding an animation tool, which is optimized for animating the simulation results. The separation of the server machine from the simulation-running machine improves the service quality by increasing the capacity to serve more requests simultaneously with even reduced web response time, and allows the execution of large scale, time-consuming simulation jobs on the powerful workstation cluster. With the addition of an animation tool, the cyber infrastructure automatically converts, upon the selection of the user, some simulation results into an animation file that can be viewed on usual web browsers without requiring installation of any special software on the user computer. Since animation is essential for understanding the results of chemical dynamics simulations, this animation capacity provides a better way for understanding simulation details of the chemical dynamics. By combining computing resources at locations under different administrative controls, this cyber infrastructure constitutes a grid environment providing physically and administratively distributed functionalities through a single easy-to-use online portal

  6. Some Mid-Life Ruminations on the Human Capacity to Transcend One's Acculturation.

    Science.gov (United States)

    Rousseve, Ronald J.

    1983-01-01

    The dialectical capacity of human consciousness enables us to generate alternatives in opposition to previous conditioning. Transcending one's acculturation need not leave one searching for gurus. Authentic personal meaning may be attained from an existential reawakening. (RM)

  7. Cortical plasticity, contingent negative variation, and transcendent experiences during practice of the Transcendental Meditation technique.

    Science.gov (United States)

    Travis, F; Tecce, J J; Guttman, J

    2000-11-01

    This study investigated effects of transcendent experiences on contingent negative variation (CNV) amplitude, CNV rebound, and distraction effects. Three groups of age-matched subjects with few (memory task in the S(1)-S(2) interval). Late CNV amplitudes in the simple trials were smallest in the group with fewest, and largest in the group with most frequent transcendent experiences. Conversely, CNV distraction effects were largest in the group with fewest and smallest in the group with most frequent transcendent experiences (the second group's values were in the middle in each case). These data suggest cumulative effects of transcendent experiences on cortical preparatory response (heightened late CNV amplitude in simple trials) and executive functioning (diminished distraction effects in letter trials).

  8. Simulating Quantum Chemical Dynamics with Improved Superconducting Qubits

    Science.gov (United States)

    Megrant, Anthony E.

    quantum dynamics resulting from a collision between Na and He atoms by encoding the problem into a time-dependent multi-qubit interaction. We compute a scattering cross section by measuring the probability of exciting the Na atom over a wide range of collision parameters. The scattering cross-section shows that there is a velocity where the excitation probability is maximized, in agreement with scattering experiments.

  9. Brownian dynamics simulations of an idealized chemical reaction network under spatial confinement and crowding conditions

    CERN Document Server

    Bellesia, Giovanni

    2015-01-01

    We investigate, via Brownian dynamics simulations, the reaction dynamics of a simple, non-linear chemical network (the Willamowski-Rossler network) under spatial confinement and crowding conditions. Our results show that the presence of inert crowders has a non-nontrivial effect on the dynamics of the network and, consequently, that effective modeling efforts aiming at a general understanding of the behavior of biochemical networks in vivo should be stochastic in nature and based on an explicit representation of both spatial confinement and macromolecular crowding.

  10. Promotion of Self-Transcendence in a Multiple Sclerosis Peer Support Groups

    Directory of Open Access Journals (Sweden)

    Tahereh Ashktorab

    2014-05-01

    Full Text Available Background: Self-transcendence can organize the challenges of multiple sclerosis patients to achieve and maintain a constant state of well-being and sense of integrity in the disease process. As a research based on self-transcendence didn't done in Iran, the present study was conducted to evaluate the effectiveness of peer groups on promoting selftranscendence level in multiple sclerosis (MS patients. Materials and Methods: This study is a before and after quasi-experimental study that was conducted on 33 patients with confirmed MS participated in three peer support groups: 10 men in male group, 11 women in female group and 12 men and women in mixed group. Eight weekly sessions and each session was 2 hours were held. Data collection tool was Self-Transcendence Scale (STS with 15 item and Cronbach's coefficient was 0.68 that after modifying, it increased to 0.81. Patients completed self administered questionnaires pre- and post of sessions. Results: Results showed that peer support groups promote the self-transcendence (p=0.001 with increases in mean self-transcendence scores in all 3 groups (men group: 0.008, women group 0.005 and mixed group: 0.003. Comparing scores before and after intervention demonstrated that self-transcendence increased equally in all groups. Conclusion: The results showed an improving in self-transcendence in peer support group participants at the end of the intervention. The results can be used in areas of nursing education and management. It is proposed that the self-transcendence assessment to be done in other chronic disease in order to evaluate its efficiency.

  11. Dynamic optimization of chemical cleaning in dead-end ultra filtration

    NARCIS (Netherlands)

    Zondervan, Edwin; Roffel, Brian

    2008-01-01

    In this paper a control strategy is formulated that minimizes the costs for a single chemical cleaning of a dead-end ultra filtration membrane. From the process model, the performance index and the constraints it can be derived that dynamic optimization will lead to a 'maximum effort control problem

  12. Spiritual Transcendence and Psychological Adjustment: The Moderating Role of Personality in Burn Patients.

    Science.gov (United States)

    Jibeen, Tahira; Mahfooz, Musferah; Fatima, Shamem

    2017-08-30

    The current study examined the moderating role of personality traits (neuroticism and extraversion) on the relationship between spiritual transcendence and positive change, and spiritual transcendence and distress in burn patients. The sample (N = 98) comprised adult burn patients (age = 25-50) admitted to three hospitals in Lahore, Pakistan. They were assessed according to a demographic information sheet, the NEO Personality Inventory (McCrae and Costa in J Personal Soc Psychol 52:81-90, 1987), the Spiritual Transcendence Index (Seidlitz et al. in J Sci Study Relig 41:439-453, 2002), the Depression, Anxiety, Stress Scales-21 (Lovibond and Lovibond in Manual for the Depression Anxiety Stress scales, Psychology Foundation, Sydney, 1995), and the Perceived Benefit Scales (McMillen and Fisher in Soc Work Res 22(3):173-186, 1998). Stepwise moderated regression analysis showed that both personality traits (neuroticism and extraversion) played a moderating role in the relationship between spiritual transcendence and positive change, and spiritual transcendence and distress in burn patients. The findings highlight the potential role spiritual transcendence may have in understanding and improving the psychological adjustment of burn patients.

  13. Orbital-specific mapping of chemical dynamics with ultrafast x-rays

    Science.gov (United States)

    Wernet, Philippe

    Charge and spin density changes at the metal sites of transition-metal complexes and in metalloproteins determine reactivity and selectivity. To understand their function and to optimize complexes for photocatalytic applications the changes of charge and spin densities need to be mapped and ultimately controlled. I will discuss how time-resolved soft x-ray spectroscopy enables a fundamental understanding of local atomic and intermolecular interactions and their dynamics on atomic length and time scales of Ångströms and femtoseconds. The approach consists in using time-resolved, atom- and orbital-specific x-ray spectroscopy and quantum chemical theory to map the frontier-orbital interactions and their evolution in real time of ultrafast chemical transformations. We recently used femtosecond resonant inelastic x-ray scattering (RIXS, the x-ray analog of resonant Raman scattering) at the x-ray free-electron laser LINAC Coherent Light Source (LCLS, Stanford, USA) to probe the reaction dynamics of a transition-metal complex in solution on the femtosecond time scale. Spin crossover and ligation are found to define the excited-state dynamics. It is demonstrated how correlating orbital symmetry and orbital interactions with spin multiplicity allows for determining the reactivity of short-lived reaction intermediates. I will discuss how this complements approaches that probe structural dynamics and how it can be extended to map the local chemical interactions and their dynamical evolution in metalloproteins.

  14. Interdependence of conformational and chemical reaction dynamics during ion assembly in polar solvents.

    Science.gov (United States)

    Ji, Minbiao; Hartsock, Robert W; Sun, Zheng; Gaffney, Kelly J

    2011-10-01

    We have utilized time-resolved vibrational spectroscopy to study the interdependence of the conformational and chemical reaction dynamics of ion assembly in solution. We investigated the chemical interconversion dynamics of the LiNCS ion pair and the (LiNCS)(2) ion-pair dimer, as well as the spectral diffusion dynamics of these ionic assemblies. For the strongly coordinating Lewis base solvents benzonitrile, dimethyl carbonate, and ethyl acetate, we observe Li(+) coordination by both solvent molecules and NCS(-) anions, while the weak Lewis base solvent nitromethane shows no evidence for solvent coordination of Li(+) ions. The strong interaction between the ion-pair dimer structure and the Lewis base solvents leads to ion-pair dimer solvation dynamics that proceed more slowly than the ion-pair dimer dissociation. We have attributed the slow spectral diffusion dynamics to electrostatic reorganization of the solvent molecules coordinated to the Li(+) cations present in the ion-pair dimer structure and concluded that the dissociation of ion-pair dimers depends more critically on longer length scale electrostatic reorganization. This unusual inversion of the conformational and chemical reaction rates does not occur for ion-pair dimer dissociation in nitromethane or for ion pair association in any of the solvents.

  15. Transcending the caesura: reverie, dreaming and counter-dreaming.

    Science.gov (United States)

    Bergstein, Avner

    2013-08-01

    The author reflects about our capacity to get in touch with primitive, irrepresentable, seemingly unreachable parts of the Self and with the unrepressed unconscious. It is suggested that when the patient's dreaming comes to a halt, or encounters a caesura, the analyst dreams that which the patient cannot. Getting in touch with such primitive mental states and with the origin of the Self is aspired to, not so much for discovering historical truth or recovering unconscious content, as for generating motion between different parts of the psyche. The movement itself is what expands the mind and facilitates psychic growth. Bion's brave and daring notion of 'caesura', suggesting a link between mature emotions and thinking and intra-uterine life, serves as a model for bridging seemingly unbridgeable states of mind. Bion inspires us to 'dream' creatively, to let our minds roam freely, stressing the analyst's speculative imagination and intuition often bordering on hallucination. However, being on the seam between conscious and unconscious, dreaming subverts the psychic equilibrium and poses a threat of catastrophe as a result of the confusion it affords between the psychotic and the non-psychotic parts of the personality. Hence there is a tendency to try and evade it through a more saturated mode of thinking, often relying on external reality. The analyst's dreaming and intuition, perhaps a remnant of intra-uterine life, is elaborated as means of penetrating and transcending the caesura, thus facilitating patient and analyst to bear unbearable states of mind and the painful awareness of the unknowability of the emotional experience. This is illustrated clinically.

  16. Chemical Reaction Rates from Ring Polymer Molecular Dynamics: Theory and Practical Applications

    CERN Document Server

    Suleimanov, Yury V; Guo, Hua

    2016-01-01

    This Feature Article presents an overview of the current status of Ring Polymer Molecular Dynamics (RPMD) rate theory. We first analyze theory and its connection to quantum transition state theory. We then focus on its practical application to prototypical chemical reactions in the gas phase, which demonstrate how accurate and reliable RPMD is for calculating thermal chemical reaction rates in multifarious cases. This review serves as an important checkpoint in RPMD rate theory development, which shows that RPMD is shifting from being just one of recent novel ideas to a well-established and validated alternative to conventional techniques for calculating thermal chemical rates. We also hope it will motivate further applications of RPMD to various chemical reactions.

  17. Chemical Reaction Rate Coefficients from Ring Polymer Molecular Dynamics: Theory and Practical Applications.

    Science.gov (United States)

    Suleimanov, Yury V; Aoiz, F Javier; Guo, Hua

    2016-11-03

    This Feature Article presents an overview of the current status of ring polymer molecular dynamics (RPMD) rate theory. We first analyze the RPMD approach and its connection to quantum transition-state theory. We then focus on its practical applications to prototypical chemical reactions in the gas phase, which demonstrate how accurate and reliable RPMD is for calculating thermal chemical reaction rate coefficients in multifarious cases. This review serves as an important checkpoint in RPMD rate theory development, which shows that RPMD is shifting from being just one of recent novel ideas to a well-established and validated alternative to conventional techniques for calculating thermal chemical rate coefficients. We also hope it will motivate further applications of RPMD to various chemical reactions.

  18. Nonequilibrium Chemical Effects in Single-Molecule SERS Revealed by Ab Initio Molecular Dynamics Simulations

    Energy Technology Data Exchange (ETDEWEB)

    Fischer, Sean A.; Apra, Edoardo; Govind, Niranjan; Hess, Wayne P.; El-Khoury, Patrick Z.

    2017-02-03

    Recent developments in nanophotonics have paved the way for achieving significant advances in the realm of single molecule chemical detection, imaging, and dynamics. In particular, surface-enhanced Raman scattering (SERS) is a powerful analytical technique that is now routinely used to identify the chemical identity of single molecules. Understanding how nanoscale physical and chemical processes affect single molecule SERS spectra and selection rules is a challenging task, and is still actively debated. Herein, we explore underappreciated chemical phenomena in ultrasensitive SERS. We observe a fluctuating excited electronic state manifold, governed by the conformational dynamics of a molecule (4,4’-dimercaptostilbene, DMS) interacting with a metallic cluster (Ag20). This affects our simulated single molecule SERS spectra; the time trajectories of a molecule interacting with its unique local environment dictates the relative intensities of the observable Raman-active vibrational states. Ab initio molecular dynamics of a model Ag20-DMS system are used to illustrate both concepts in light of recent experimental results.

  19. Chemical Composition and Dynamics of the Upper Troposphere and the Lower Stratosphere: Overview of the Project

    Science.gov (United States)

    Sofieva, V. F.; Liu, C.; Huang, F.; Kyrola, E.; Liu, Y.; Ialongo, I.; Hakkarainen, J.; Zhang, Y.

    2016-08-01

    The DRAGON-3 cooperation study on the upper troposphere and the lower stratosphere (UTLS) is based on new satellite data and modern atmospheric models. The objectives of the project are: (i) assessment of satellite data on chemical composition in UTLS, (ii) dynamical and chemical structures of the UTLS and its variability, (iii) multi-scale variability of stratospheric ozone, (iv) climatology of the stratospheric aerosol layer and its variability, and (v) updated ozone climatology and its relation to tropopause/multiple tropopauses.In this paper, we present the main results of the project.

  20. State-to-state dynamics of elementary chemical reactions using Rydberg H-atom translational spectroscopy

    Science.gov (United States)

    Yang, Xueming

    In this review, a few examples of state-to-state dynamics studies of both unimolecular and bimolecular reactions using the H-atom Rydberg tagging TOF technique were presented. From the H2O photodissociation at 157 nm, a direction dissociation example is provided, while photodissociation of H2O at 121.6 has provided an excellent dynamical case of complicated, yet direct dissociation process through conical intersections. The studies of the O(1D) + H2 → OH + H reaction has also been reviewed here. A prototype example of state-to-state dynamics of pure insertion chemical reaction is provided. Effect of the reagent rotational excitation and the isotope effect on the dynamics of this reaction have also been investigated. The detailed mechanism for abstraction channel in this reaction has also been closely studied. The experimental investigations of the simplest chemical reaction, the H3 system, have also been described here. Through extensive collaborations between theory and experiment, the mechanism for forward scattering product at high collision energies for the H + HD reaction was clarified, which is attributed to a slow down mechanism on the top of a quantized barrier transition state. Oscillations in the product quantum state resolved different cross sections have also been observed in the H + D2 reaction, and were attributed to the interference of adiabatic transition state pathways from detailed theoretical analysis. The results reviewed here clearly show the significant advances we have made in the studies of the state-to-state molecular reaction dynamics.

  1. Chemical spots and their dynamical evolution on HgMn stars

    CERN Document Server

    Korhonen, Heidi; Briquet, Maryline; Gonzalez, Federico; Savanov, Igor

    2010-01-01

    Our recent studies of late B-type stars with HgMn peculiarity revealed for the first time the presence of fast dynamical evolution of chemical spots on their surfaces. These observations suggest a hitherto unknown physical process operating in the stars with radiative outer envelopes. Furthermore, we have also discovered existence of magnetic fields on these stars that have up to now been thought to be non-magnetic. Here we will discuss the dynamical spot evolution on HD 11753 and our new results on magnetic fields on AR Aur.

  2. Integrating molecular dynamics simulations with chemical probing experiments using SHAPE-FIT

    Science.gov (United States)

    Kirmizialtin, Serdal; Hennelly, Scott P.; Schug, Alexander; Onuchic, Jose N.; Sanbonmatsu, Karissa Y.

    2016-01-01

    Integration and calibration of molecular dynamics simulations with experimental data remains a challenging endeavor. We have developed a novel method to integrate chemical probing experiments with molecular simulations of RNA molecules by using a native structure-based model. Selective 2’-hydroxyl acylation by primer extension (SHAPE) characterizes the mobility of each residue in the RNA. Our method, SHAPE-FIT, automatically optimizes the potential parameters of the forcefield according to measured reactivities from SHAPE. The optimized parameter set allows simulations of dynamics highly consistent with SHAPE probing experiments. Such atomistic simulations, thoroughly grounded in experiment, can open a new window on RNA structure-function relations. PMID:25726467

  3. Chemical process dynamic optimization based on the differential evolution algorithm with an adaptive scheduling mutation strategy

    Science.gov (United States)

    Zhu, Jun; Yan, Xuefeng; Zhao, Weixiang

    2013-10-01

    To solve chemical process dynamic optimization problems, a differential evolution algorithm integrated with adaptive scheduling mutation strategy (ASDE) is proposed. According to the evolution feedback information, ASDE, with adaptive control parameters, adopts the round-robin scheduling algorithm to adaptively schedule different mutation strategies. By employing an adaptive mutation strategy and control parameters, the real-time optimal control parameters and mutation strategy are obtained to improve the optimization performance. The performance of ASDE is evaluated using a suite of 14 benchmark functions. The results demonstrate that ASDE performs better than four conventional differential evolution (DE) algorithm variants with different mutation strategies, and that the whole performance of ASDE is equivalent to a self-adaptive DE algorithm variant and better than five conventional DE algorithm variants. Furthermore, ASDE was applied to solve a typical dynamic optimization problem of a chemical process. The obtained results indicate that ASDE is a feasible and competitive optimizer for this kind of problem.

  4. A review of dynamical resonances in A  +  BC chemical reactions

    Science.gov (United States)

    Ren, Zefeng; Sun, Zhigang; Zhang, Donghui; Yang, Xueming

    2017-02-01

    The concept of the transition state has played an important role in the field of chemical kinetics and reaction dynamics. Reactive resonances in the transition-state region can dramatically enhance the reaction probability; thus investigation of the reactive resonances has attracted great attention from chemical physicists for many decades. In this review, we mainly focus on the recent progress made in probing the elusive resonance phenomenon in the simple A  +  BC reaction and understanding its nature, especially in the benchmark F/Cl  +  H2 and their isotopic variants. The signatures of reactive resonances in the integral cross section, differential cross section (DCS), forward- and backward-scattered DCS, and anion photodetachment spectroscopy are comprehensively presented in individual prototype reactions. The dynamical origins of reactive resonances are also discussed in this review, based on information on the wave function in the transition-state region obtained by time-dependent quantum wave-packet calculations.

  5. Oral dosing of chemical indicators for in vivo monitoring of Ca2+ dynamics in insect muscle.

    Science.gov (United States)

    Ferdinandus; Arai, Satoshi; Ishiwata, Shin'ichi; Suzuki, Madoka; Sato, Hirotaka

    2015-01-01

    This paper proposes a remarkably facile staining protocol to visually investigate dynamic physiological events in insect tissues. We attempted to monitor Ca2+ dynamics during contraction of electrically stimulated living muscle. Advances in circuit miniaturization and insect neuromuscular physiology have enabled the hybridization of living insects and man-made electronic components, such as microcomputers, the result of which has been often referred as a Living Machine, Biohybrid, or Cyborg Insect. In order for Cyborg Insects to be of practical use, electrical stimulation parameters need to be optimized to induce desired muscle response (motor action) and minimize the damage in the muscle due to the electrical stimuli. Staining tissues and organs as well as measuring the dynamics of chemicals of interest in muscle should be conducted to quantitatively and systematically evaluate the effect of various stimulation parameters on the muscle response. However, existing staining processes require invasive surgery and/or arduous procedures using genetically encoded sensors. In this study, we developed a non-invasive and remarkably facile method for staining, in which chemical indicators can be orally administered (oral dosing). A chemical Ca2+ indicator was orally introduced into an insect of interest via food containing the chemical indicator and the indicator diffused from the insect digestion system to the target muscle tissue. We found that there was a positive relationship between the fluorescence intensity of the indicator and the frequency of electrical stimulation which indicates the orally dosed indicator successfully monitored Ca2+ dynamics in the muscle tissue. This oral dosing method has a potential to globally stain tissues including neurons, and investigating various physiological events in insects.

  6. Ego and Spiritual Transcendence: Relevance to Psychological Resilience and the Role of Age

    Directory of Open Access Journals (Sweden)

    Barbara Hanfstingl

    2013-01-01

    Full Text Available The paper investigates different approaches of transcendence in the sense of spiritual experience as predictors for general psychological resilience. This issue is based on the theoretical assumption that resilience does play a role for physical health. Furthermore, there is a lack of empirical evidence about the extent to which spirituality does play a role for resilience. As potential predictors for resilience, ego transcendence, spiritual transcendence, and meaning in life were measured in a sample of 265 people. The main result of a multiple regression analysis is that, in the subsample with people below 29 years, only one rather secular scale that is associated with ego transcendence predicts resilience, whereas for the older subsample of 29 years and above, spiritual transcendence gains both a positive (oneness and timelessness and a negative (spiritual insight relevance to psychological resilience. On the one hand, these results concur with previous studies that also found age-related differences. On the other hand, it is surprising that the MOS spiritual insight predicts psychological resilience negatively, the effect is increasing with age. One possible explanation concerns wisdom research. Here, an adaptive way of dealing with the age-related loss of control is assumed to be relevant to successful aging.

  7. The effect of self-transcendence on depression in cognitively intact nursing home patients.

    Science.gov (United States)

    Haugan, Gørill; Innstrand, Siw Tone

    2012-01-01

    Aims. This study's aim was to test the effects of self-transcendence on depression among cognitively intact nursing home patients. Background. Depression is considered the most frequent mental disorder among the elderly population. Specifically, the depression rate among nursing home patients is three to four times higher than that among community-dwelling elderly. Therefore, finding new and alternative ways to prevent and decrease depression is of great importance for nursing home patients' well-being. Self-transcendence is related to spiritual as well as nonspiritual factors, and it is described as a correlate and resource for well-being among vulnerable populations and at the end of life. Methods. A two-factor construct of the self-transcendence scale (interpersonal and intrapersonal) and the hospital anxiety and depression scale (HADS) was applied. A sample of 202 cognitively intact nursing home patients in central Norway was selected to respond to the questionnaires in 2008/2009. Results. A hypothesized SEM model demonstrated significant direct relationships and total effects of self-transcendence on depression. Conclusion and Implication for Practice. Facilitating patients' self-transcendence, both interpersonally and intrapersonally, might decrease depression among cognitively intact nursing home patients.

  8. Effect of dynamic operation on chemical degradation of a polymer electrolyte membrane fuel cell

    Science.gov (United States)

    Jung, Minjae; Williams, Keith A.

    2011-03-01

    Dynamic operation is known as one of the factors for accelerating chemical degradation of the polymer electrolyte membrane in a polymer electrolyte membrane fuel cell (PEMFC). However, little effort has been made dealing with the quantification of the degradation process. In this investigation, cyclic current operation is carried out on a fuel cell system, and the frequency effect of cyclic operation on chemical degradation is investigated. The dynamic behavior of a fuel cell system is analyzed first with the modified Randles model, where the charge double layer is modeled by three components; a charge transfer resistance (Rct), and two RC cells for the Warburg impedance. After calculating each parameter value through exponential curve fitting, the dynamic behaviors of the three components are simulated using MATLAB Simulink®. Fluoride release as a function of the frequency of cyclic operation is evaluated by measuring the concentration of fluoride ion in effluent from a fuel cell exhaust. The frequency effect on chemical degradation is explained by comparing the simulated results and the fluoride release results. Two possible reasons for the accelerated degradation at cyclic operation are also suggested.

  9. Fast Atomic-Scale Chemical Imaging of Crystalline Materials and Dynamic Phase Transformations.

    Science.gov (United States)

    Lu, Ping; Yuan, Ren Liang; Ihlefeld, Jon F; Spoerke, Erik David; Pan, Wei; Zuo, Jian Min

    2016-04-13

    Atomic-scale phenomena fundamentally influence materials form and function that makes the ability to locally probe and study these processes critical to advancing our understanding and development of materials. Atomic-scale chemical imaging by scanning transmission electron microscopy (STEM) using energy-dispersive X-ray spectroscopy (EDS) is a powerful approach to investigate solid crystal structures. Inefficient X-ray emission and collection, however, require long acquisition times (typically hundreds of seconds), making the technique incompatible with electron-beam sensitive materials and study of dynamic material phenomena. Here we describe an atomic-scale STEM-EDS chemical imaging technique that decreases the acquisition time to as little as one second, a reduction of more than 100 times. We demonstrate this new approach using LaAlO3 single crystal and study dynamic phase transformation in beam-sensitive Li[Li0.2Ni0.2Mn0.6]O2 (LNMO) lithium ion battery cathode material. By capturing a series of time-lapsed chemical maps, we show for the first time clear atomic-scale evidence of preferred Ni-mobility in LNMO transformation, revealing new kinetic mechanisms. These examples highlight the potential of this approach toward temporal, atomic-scale mapping of crystal structure and chemistry for investigating dynamic material phenomena.

  10. Dynamics, Miscibility, and Morphology in Polymer-Molecule Blends: The Impact of Chemical Functionality

    KAUST Repository

    Do, Khanh

    2015-10-22

    In the quest to improve the performance of organic bulk-heterojunction solar cells, many recent efforts have focused on developing molecular and polymer alternatives to commonly used fullerene acceptors. Here, molecular dynamics simulations are used to investigate polymer-molecule blends comprised of the polymer donor poly(3-hexylthiophene) (P3HT) with a series of acceptors based on trialkylsilylethynyl-substituted pentacene. A matrix of nine pentacene derivatives, consisting of systematic chemical variation both in the nature of the alkyl groups and electron-withdrawing moieties appended to the acene, is used to draw connections between the chemical structure of the acene acceptor and the nanoscale properties of the polymer-molecule blend. These connections include polymer and molecular diffusivity, donor-acceptor packing and interfacial (contact) area, and miscibility. The results point to the very significant role that seemingly modest changes in chemical structure play during the formation of polymer-molecule blend morphologies.

  11. Chemical and biological activity in open flows: A dynamical system approach

    Energy Technology Data Exchange (ETDEWEB)

    Tel, Tamas [Institute for Theoretical Physics, Eoetvoes University, P.O. Box 32, H-1518, Budapest (Hungary); Moura, Alessandro de [Instituto de Fisica, Universidade de Sao Paulo, Caixa Postal 66318, 05315-970, Sao Paulo, SP (Brazil); Grebogi, Celso [Instituto de Fisica, Universidade de Sao Paulo, Caixa Postal 66318, 05315-970, Sao Paulo, SP (Brazil) and Max-Plank-Institute for the Physics of Complex Systems, Noethnitzer Str. 38, D-01187 Dresden (Germany)]. E-mail: grebogi@if.usp.br; Karolyi, Gyoergy [Center for Applied Mathematics and Computational Physics, and Department of Structural Mechanics, Budapest University of Technology and Economics, Mueegyetem rkp. 3, H-1521, Budapest (Hungary)

    2005-07-01

    Chemical and biological processes often take place in fluid flows. Many of them, like environmental or microfluidical ones, generate filamentary patterns which have a fractal structure, due to the presence of chaos in the underlying advection dynamics. In such cases, hydrodynamical stirring strongly couples to the reactivity of the advected species: the outcome of the reaction is then typically different from that of the same reaction taking place in a well-mixed environment. Here we review recent progress in this field, which became possible due to the application of methods taken from dynamical system theory. We place special emphasis on the derivation of effective rate equations which contain singular terms expressing the fact that the reaction takes place on a moving fractal catalyst, on the unstable foliation of the reaction free advection dynamics.

  12. Transcendence in the current theology, philosophy and metaphysics in Russian cosmism

    Directory of Open Access Journals (Sweden)

    Emanuel George Oprea

    2016-03-01

    Full Text Available Human interests to Religion and Metaphysics are well explained by the desire of the people to answer to fundamental and eternal questions as “what is the sense of life” and “what is the purpose of life”. These questions have accompanied them from the beginning of conscious life. Many intellectuals, scientists and writers of former USSR and democratic Russia have brought essential contributions, opened new directions and finally have enriched with new concepts, ideas, ideologies and systems the worldwide Philosophy and Religion. A possible answer is the Creation allowing to Divinity to transcend in common life. Soul as Spiritual reflection of Divinity tends to perfection, reiterating in every generation the transcendence to God. At first sight there are no meeting points between Transcendence and Cosmism because the last notion has its beginning in the progress of Science. The evolution of modern Sciences, philosophical concepts and Religion gradually demonstrates correlated aspects which must be discovered in the future.

  13. Self-transcendence facilitates meaning-making and flow: Evidence from a pilot experimental study

    Directory of Open Access Journals (Sweden)

    Osin, Evgeny N.

    2016-06-01

    Full Text Available We review the psychological theory of flow and focus on the notion of the autotelic personality, arguing that self-transcendence (understood within the existential tradition of Frankl and Längle as the individual’s ability to establish inner relationships with values can be viewed as a personality disposition conducive to flow experience. The study aimed to investigate the effects of situational task meaning and dispositional self-transcendence on productivity and flow experience. We present a pilot quasi-experimental study conducted in a student sample (N = 82 Students were asked to work in small-group settings on a creative task, which consisted in finding solutions to a social problem. Each group was randomly assigned to an instruction presenting the problem as happening either in a distant country (low-meaning or in their home country (high-meaning condition. The outcome variables were measures of flow, perceived meaning of the task, and satisfaction with time spent working. The solutions generated by the students were rated by three experts. The experimental manipulation had a main effect on the quality of the resulting solutions, but not on the subjective experience of the participants. A number of significant interaction effects were found, indicating that the associations of self-transcendence with experiential outcomes tended to be linear under the low-meaning condition, but curvilinear under the high-meaning condition. The findings suggest that self-transcendence is particularly beneficial to flow in situations with unclear meaning, but very high levels of self-transcendence may hinder flow in highly meaningful situations. Overall, the findings suggest that self-transcendence can be considered as a disposition of the autotelic personality.

  14. Tight-binding quantum chemical molecular dynamics simulations for the elucidation of chemical reaction dynamics in SiC etching with SF6/O2 plasma.

    Science.gov (United States)

    Ito, Hiroshi; Kuwahara, Takuya; Kawaguchi, Kentaro; Higuchi, Yuji; Ozawa, Nobuki; Kubo, Momoji

    2016-03-21

    We used our etching simulator [H. Ito et al., J. Phys. Chem. C, 2014, 118, 21580-21588] based on tight-binding quantum chemical molecular dynamics (TB-QCMD) to elucidate SiC etching mechanisms. First, the SiC surface is irradiated with SF5 radicals, which are the dominant etchant species in experiments, with the irradiation energy of 300 eV. After SF5 radicals bombard the SiC surface, Si-C bonds dissociate, generating Si-F, C-F, Si-S, and C-S bonds. Then, etching products, such as SiS, CS, SiFx, and CFx (x = 1-4) molecules, are generated and evaporated. In particular, SiFx is the main generated species, and Si atoms are more likely to vaporize than C atoms. The remaining C atoms on SiC generate C-C bonds that may decrease the etching rate. Interestingly, far fewer Si-Si bonds than C-C bonds are generated. We also simulated SiC etching with SF3 radicals. Although the chemical reaction dynamics are similar to etching with SF5 radicals, the etching rate is lower. Next, to clarify the effect of O atom addition on the etching mechanism, we also simulated SiC etching with SF5 and O radicals/atoms. After bombardment with SF5 radicals, Si-C bonds dissociate in a similar way to the etching without O atoms. In addition, O atoms generate many C-O bonds and COy (y = 1-2) molecules, inhibiting the generation of C-C bonds. This indicates that O atom addition improves the removal of C atoms from SiC. However, for a high O concentration, many C-C and Si-Si bonds are generated. When the O atoms dissociate the Si-C bonds and generate dangling bonds, the O atoms terminate only one or two dangling bonds. Moreover, at high O concentrations there are fewer S and F atoms to terminate the dangling bonds than at low O concentration. Therefore, few dangling bonds of dissociated Si and C atoms are terminated, and they form many Si-Si and C-C bonds. Furthermore, we propose that the optimal O concentration is 50-60% because both Si and C atoms generate many etching products producing fewer C

  15. Dynamic Chemically Driven Dewetting, Spreading, and Self-Running of Sessile Droplets on Crystalline Silicon.

    Science.gov (United States)

    Arscott, Steve

    2016-12-06

    A chemically driven dewetting effect is demonstrated using sessile droplets of dilute hydrofluoric acid on chemically oxidized silicon wafers. The dewetting occurs as the thin oxide is slowly etched by the droplet and replaced by a hydrogen-terminated surface; the result of this is a gradual increase in the contact angle of the droplet with time. The time-varying work of adhesion is calculated from the time-varying contact angle; this corresponds to the changing chemical nature of the surface during dewetting and can be modeled by the well-known logistic (sigmoid) function often used for the modeling of restricted growth, in this case, the transition from an oxidized surface to a hydrogen-terminated silicon surface. The observation of the time-varying contact angle allows one to both measure the etch rate of the silicon oxide and estimate the hydrogenation rate as a function of HF concentration and wafer type. In addition to this, at a certain HF concentration, a self-running droplet effect is observed. In contrast, on hydrogen-terminated silicon wafers, a chemically induced spreading effect is observed using sessile droplets of nitric acid. The droplet spreading can also be modeled using a logistical function, where the restricted growth is the transition from hydrogen-terminated to a chemically induced oxidized silicon surface. The chemically driven dewetting and spreading observed here add to the methods available to study dynamic wetting (e.g., the moving three-phase contact line) of sessile droplets on surfaces. By slowing down chemical kinetics of the wetting, one is able to record the changing profile of the sessile droplet with time and gather information concerning the time-varying surface chemistry. The data also indicates a chemical interface hysteresis (CIH) that is compared to contact angle hysteresis (CAH). The approach can also be used to study the chemical etching and deposition behavior of thin films using liquids by monitoring the macroscopic

  16. Toward Chemically Resolved Computer Simulations of Dynamics and Remodeling of Biological Membranes.

    Science.gov (United States)

    Soares, Thereza A; Vanni, Stefano; Milano, Giuseppe; Cascella, Michele

    2017-08-03

    Cellular membranes are fundamental constituents of living organisms. Apart from defining the boundaries of the cells, they are involved in a wide range of biological functions, associated with both their structural and the dynamical properties. Biomembranes can undergo large-scale transformations when subject to specific environmental changes, including gel-liquid phase transitions, change of aggregation structure, formation of microtubules, or rupture into vesicles. All of these processes are dependent on a delicate interplay between intermolecular forces, molecular crowding, and entropy, and their understanding requires approaches that are able to capture and rationalize the details of all of the involved interactions. Molecular dynamics-based computational models at atom-level resolution are, in principle, the best way to perform such investigations. Unfortunately, the relevant spatial and time dimensionalities involved in membrane remodeling phenomena would require computational costs that are today unaffordable on a routinely basis. Such hurdles can be removed by coarse-graining the representations of the individual molecular components of the systems. This procedure anyway reduces the possibility of describing the chemical variations in the lipid mixtures composing biological membranes. New hybrid particle field multiscale approaches offer today a promising alternative to the more traditional particle-based simulations methods. By combining chemically distinguishable molecular representations with mesoscale-based computationally affordable potentials, they appear as one of the most promising ways to keep an accurate description of the chemical complexity of biological membranes and, at the same time, cover the required scales to describe remodeling events.

  17. Small Open Chemical Systems Theory: Its Implications to Darwinian Evolution Dynamics, Complex Self-Organization and Beyond

    National Research Council Canada - National Science Library

    QIAN Hong

    2014-01-01

    The study of biological cells in terms of mesoscopic, nonequilibrium, nonlinear, stochastic dynamics of open chemical systems provides a paradigm for other complex, self-organizing systems with ultra...

  18. Automatic differentiation tools in the dynamic simulation of chemical engineering processes

    Directory of Open Access Journals (Sweden)

    Castro M.C.

    2000-01-01

    Full Text Available Automatic Differentiation is a relatively recent technique developed for the differentiation of functions applicable directly to the source code to compute the function written in standard programming languages. That technique permits the automatization of the differentiation step, crucial for dynamic simulation and optimization of processes. The values for the derivatives obtained with AD are exact (to roundoff. The theoretical exactness of the AD comes from the fact that it uses the same rules of differentiation as in differential calculus, but these rules are applied to an algorithmic specification of the function rather than to a formula. The main purpose of this contribution is to discuss the impact of Automatic Differentiation in the field of dynamic simulation of chemical engineering processes. The influence of the differentiation technique on the behavior of the integration code, the performance of the generated code and the incorporation of AD tools in consistent initialization tools are discussed from the viewpoint of dynamic simulation of typical models in chemical engineering.

  19. Self-organized mechano-chemical dynamics in amoeboid locomotion of Physarum fragments

    Science.gov (United States)

    Zhang, Shun; Guy, Robert D.; Lasheras, Juan C.; del Álamo, Juan C.

    2017-05-01

    The aim of this work is to quantify the spatio-temporal dynamics of flow-driven amoeboid locomotion in small (∼100 μm) fragments of the true slime mold Physarum polycephalum. In this model organism, cellular contraction drives intracellular flows, and these flows transport the chemical signals that regulate contraction in the first place. As a consequence of these non-linear interactions, a diversity of migratory behaviors can be observed in migrating Physarum fragments. To study these dynamics, we measure the spatio-temporal distributions of the velocities of the endoplasm and ectoplasm of each migrating fragment, the traction stresses it generates on the substratum, and the concentration of free intracellular calcium. Using these unprecedented experimental data, we classify migrating Physarum fragments according to their dynamics, finding that they often exhibit spontaneously coordinated waves of flow, contractility and chemical signaling. We show that Physarum fragments exhibiting symmetric spatio-temporal patterns of endoplasmic flow migrate significantly slower than fragments with asymmetric patterns. In addition, our joint measurements of ectoplasm velocity and traction stress at the substratum suggest that forward motion of the ectoplasm is enabled by a succession of stick-slip transitions, which we conjecture are also organized in the form of waves. Combining our experiments with a simplified convection-diffusion model, we show that the convective transport of calcium ions may be key for establishing and maintaining the spatio-temporal patterns of calcium concentration that regulate the generation of contractile forces.

  20. Towards Cluster-Assembled Materials of True Monodispersity in Size and Chemical Environment: Synthesis, Dynamics and Activity

    Science.gov (United States)

    2016-10-27

    pathway Status: not yet published Diverse technologies, from catalyst coking to graphene synthesis , entail hydrocarbon dehydrogena- tion and...AFRL-AFOSR-UK-TR-2016-0037 Towards cluster-assembled materials of true monodispersity in size and chemical environment: Synthesis , Dynamics and...Towards cluster-assembled materials of true monodispersity in size and chemical environment: synthesis , dynamics and activity 5a.  CONTRACT NUMBER 5b

  1. Ultrafast chemical reactions in shocked nitromethane probed with dynamic ellipsometry and transient absorption spectroscopy.

    Science.gov (United States)

    Brown, Kathryn E; McGrane, Shawn D; Bolme, Cynthia A; Moore, David S

    2014-04-10

    Initiation of the shock driven chemical reactions and detonation of nitromethane (NM) can be sensitized by the addition of a weak base; however, the chemical mechanism by which sensitization occurs remains unclear. We investigated the shock driven chemical reaction in NM and in NM sensitized with diethylenetriamine (DETA), using a sustained 300 ps shock driven by a chirped Ti:sapphire laser. We measured the solutions' visible transient absorption spectra and measured interface particle and shock velocities of the nitromethane solutions using ultrafast dynamic ellipsometry. We found there to be a volume-increasing reaction that takes place around interface particle velocity up = 2.4 km/s and up = 2.2 km/s for neat NM and NM with 5% DETA, respectively. The rate at which transient absorption increases is similar in all mixtures, but with decreasing induction times for solutions with increasing DETA concentrations. This result supports the hypothesis that the chemical reaction mechanisms for shocked NM and NM with DETA are the same. Data from shocked NM are compared to literature experimental and theoretical data.

  2. Incorporating chemical modification constraints into a dynamic programming algorithm for prediction of RNA secondary structure

    Science.gov (United States)

    Mathews, David H.; Disney, Matthew D.; Childs, Jessica L.; Schroeder, Susan J.; Zuker, Michael; Turner, Douglas H.

    2004-01-01

    A dynamic programming algorithm for prediction of RNA secondary structure has been revised to accommodate folding constraints determined by chemical modification and to include free energy increments for coaxial stacking of helices when they are either adjacent or separated by a single mismatch. Furthermore, free energy parameters are revised to account for recent experimental results for terminal mismatches and hairpin, bulge, internal, and multibranch loops. To demonstrate the applicability of this method, in vivo modification was performed on 5S rRNA in both Escherichia coli and Candida albicans with 1-cyclohexyl-3-(2-morpholinoethyl) carbodiimide metho-p-toluene sulfonate, dimethyl sulfate, and kethoxal. The percentage of known base pairs in the predicted structure increased from 26.3% to 86.8% for the E. coli sequence by using modification constraints. For C. albicans, the accuracy remained 87.5% both with and without modification data. On average, for these sequences and a set of 14 sequences with known secondary structure and chemical modification data taken from the literature, accuracy improves from 67% to 76%. This enhancement primarily reflects improvement for three sequences that are predicted with <40% accuracy on the basis of energetics alone. For these sequences, inclusion of chemical modification constraints improves the average accuracy from 28% to 78%. For the 11 sequences with <6% pseudoknotted base pairs, structures predicted with constraints from chemical modification contain on average 84% of known canonical base pairs. PMID:15123812

  3. Study on interface behavior of 3D composites reinforced with chemically connected CNTs using molecular dynamics

    Science.gov (United States)

    Yang, Lin; He, Xiaodong; Tong, Liyong

    2009-07-01

    In this study, we used several molecular dynamic models to simulate the pull-out process of a carbon nanotube (CNT) that is assumed to be chemically connected to a carbon fiber, and to calculate the CNTs' geometry variation, displacement, energy and stress during this process. In the simulation, the CNTs' elongation and necking phenomena have been noted prior to the movement of the CNT's end embedded in resin. The simulation yields a CNT's plastic constitutive model in the pull-out process. The fracture resistance capability of a chemically connected CNT is then discussed. In the simulation of shearing, the prediction of the CNTs' capability of shear resistance has been conducted. Finally, by comparing the experiment result with the simulation, we predict the amido link break before the CNT pull-out in the shearing test.

  4. Nonlinear Stochastic Dynamics of Complex Systems, I: A Chemical Reaction Kinetic Perspective with Mesoscopic Nonequilibrium Thermodynamics

    CERN Document Server

    Qian, Hong

    2016-01-01

    We distinguish a mechanical representation of the world in terms of point masses with positions and momenta and the chemical representation of the world in terms of populations of different individuals, each with intrinsic stochasticity, but population wise with statistical rate laws in their syntheses, degradations, spatial diffusion, individual state transitions, and interactions. Such a formal kinetic system in a small volume $V$, like a single cell, can be rigorously treated in terms of a Markov process describing its nonlinear kinetics as well as nonequilibrium thermodynamics at a mesoscopic scale. We introduce notions such as open, driven chemical systems, entropy production, free energy dissipation, etc. Then in the macroscopic limit, we illustrate how two new "laws", in terms of a generalized free energy of the mesoscopic stochastic dynamics, emerge. Detailed balance and complex balance are two special classes of "simple" nonlinear kinetics. Phase transition is intrinsically related to multi-stability...

  5. Molecular dynamics study of phase separation in fluids with chemical reactions.

    Science.gov (United States)

    Krishnan, Raishma; Puri, Sanjay

    2015-11-01

    We present results from the first d=3 molecular dynamics (MD) study of phase-separating fluid mixtures (AB) with simple chemical reactions (A⇌B). We focus on the case where the rates of forward and backward reactions are equal. The chemical reactions compete with segregation, and the coarsening system settles into a steady-state mesoscale morphology. However, hydrodynamic effects destroy the lamellar morphology which characterizes the diffusive case. This has important consequences for the phase-separating structure, which we study in detail. In particular, the equilibrium length scale (ℓ(eq)) in the steady state suggests a power-law dependence on the reaction rate ε:ℓ(eq)∼ε(-θ) with θ≃1.0.

  6. Steady dynamics of exothermic chemical wave fronts in van der Waals fluids

    Science.gov (United States)

    Dumazer, G.; Antoine, C.; Lemarchand, A.; Nowakowski, B.

    2009-12-01

    We study the steady dynamics of an exothermic Fisher-Kolmogorov-Petrovsky-Piskunov chemical wave front traveling in a one-dimensional van der Waals fluid. The propagating wave is initiated by a nonuniformity in reactant concentration contrary to usual combustion ignition processes. The heat release and activation energy of the reaction play the role of control parameters. We recently proved that the propagation of an exothermic chemical wave front in a perfect gas displays a forbidden interval of stationary wave front speeds [G. Dumazer, M. Leda, B. Nowakowski, and A. Lemarchand, Phys. Rev. E 78, 016309 (2008)]. We examine how this result is modified for nonideal fluids and determine the effect of the van der Waals parameters and fluid density on the bifurcation between diffusion flames and Chapman-Jouguet detonation waves as heat release increases. Analytical predictions are confirmed by the numerical solution of the hydrodynamic equations including reaction kinetics.

  7. Shock initiated thermal and chemical responses of HMX crystal from ReaxFF molecular dynamics simulation.

    Science.gov (United States)

    Zhou, Tingting; Song, Huajie; Liu, Yi; Huang, Fenglei

    2014-07-21

    To gain an atomistic-level understanding of the thermal and chemical responses of condensed energetic materials under thermal shock, we developed a thermal shock reactive dynamics (TS-RD) computational protocol using molecular dynamics simulation coupled with ReaxFF force field. β-Octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocane (HMX) was selected as a a target explosive due to its wide usage in the military and industry. The results show that a thermal shock initiated by a large temperature gradient between the "hot" region and the "cold" region results in thermal expansion of the particles and induces a thermal-mechanical wave propagating back and forth in the system with an averaged velocity of 3.32 km s(-1). Heat propagating along the direction of thermal shock leads to a temperature increment of the system and thus chemical reaction initiation. Applying a continuum reactive heat conduction model combined with the temperature distribution obtained from the RD simulation, a heat conduction coefficient is derived as 0.80 W m(-1) K(-1). The chemical reaction mechanisms during thermal shock were analyzed, showing that the reaction is triggered by N-NO2 bond breaking followed by HONO elimination and ring fission. The propagation rates of the reaction front and reaction center are obtained to be 0.069 and 0.038 km s(-1), based on the time and spatial distribution of NO2. The pressure effect on the thermal shock was also investigated by employing uniaxial compression before the thermal shock. We find that compression significantly accelerates thermal-mechanical wave propagation and heat conduction, resulting in higher temperature and more excited molecules and thus earlier initiation and faster propagation of chemical reactions.

  8. On-line Dynamic Model Correction Based Fault Diagnosis in Chemical Processes

    Institute of Scientific and Technical Information of China (English)

    田文德; 孙素莉

    2007-01-01

    A novel fault detection and diagnosis method was proposed,using dynamic simulation to monitor chemical process and identify faults when large tracking deviations occur.It aims at parameter failures,and the parameters are updated via on-line correction.As it can predict the trend of process and determine the existence of malfunctions simultaneously,this method does not need to design problem-specific observer to estimate unmeasured state variables.Application of the proposed method is presented on one water tank and one aromatization reactor,and the results are compared with those from the traditional method.

  9. TRENDS OF CURRENT DYNAMICS OF CHEMICAL PROCESSES IN THE SOILS OF ODESSA REGION

    Directory of Open Access Journals (Sweden)

    Bilanchyn Yaroslav

    2012-06-01

    Full Text Available Results of chemical processes’ dynamic studies of many years (1971-2011 in the soils of Odessa Region have been described. The most significant in the last 15-20 years have been changes of humus content and ecological & agrochemical status of black soils. In spite of some increase in the norm of fertilizers input for the last 5 years the negative balance of plant nutrition elements in soils is preserved. Ways of optimization of humus and ecological & agrochemical status of soils in the region and increase of their fertility have been proposed.

  10. Influence of the work of adhesion on the dynamic wetting of chemically heterogeneous surfaces.

    Science.gov (United States)

    Ray, Santanu; Sedev, Rossen; Priest, Craig; Ralston, John

    2008-11-18

    The velocity dependence of the dynamic contact angle for a glycerol-water mixture wetting two different chemically heterogeneous surfaces (mixed thiols on gold and partially methylated titania, 16 samples in all) was studied. The molecular kinetic theory (MKT) of wetting was used to interpret the dynamic contact angle data. The equilibrium displacement frequency ( K 0) was predominantly determined by the viscous contribution from the bulk liquid, with a minor contribution from the surface. The mean distance between surface sites (lambda) decreased with increasing work of adhesion. The contact line friction coefficient zeta 0 was found to vary exponentially with the work of adhesion, enabling the unit flow volume of the liquid to be obtained.

  11. Studying chemical reactions in biological systems with MBN Explorer: implementation of molecular mechanics with dynamical topology

    CERN Document Server

    Sushko, Gennady B; Verkhovtsev, Alexey V; Volkov, Sergey N; Solov'yov, Andrey V

    2015-01-01

    The concept of molecular mechanics force field has nowadays been widely accepted for studying various processes in biomolecular systems. In this paper we suggest a modification for the standard CHARMM force field, that permits simulations of systems with dynamically changing molecular topologies. The implementation of the modified force field was carried out in the popular program MBN Explorer, and, to support the development, in this paper we provide several case studies where dynamical topology is necessary. In particular, it is shown, that the modified molecular mechanics force field can be applied for studying processes where rupture of chemical bonds plays an essential role, e.g., in irradiation or collision induced damage, transformation and fragmentation processes involving biomolecular systems.

  12. Analysis of forward and inverse problems in chemical dynamics and spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Rabitz, H.

    1992-01-01

    The forward aspects of the research were concerned with mapping the relation between input potential surface structure, and laboratory dynamical and kinetic observables. The research on inverse analysis complemented the forward analysis studies; objective was to develop algorithms for inversion of quality laboratory data, back to underlying potential surfaces. 24 items of research in molecular dynamics and chemical kinetics are reported. The following collisions/reactions were studied: H + H[sub 2], He - H[sub 2], He - Xe/C(0001), thermal explosions, CO/H[sub 2]/O[sub 2], H[sub 2] + HD, H[sup +] + F([sup 2]P[sub 1/2]), He[sup +] + Ne(2p[sup 6]), Na + I, F + H[sub 2], CO - H[sub 2] - O[sub 2].

  13. Analysis of forward and inverse problems in chemical dynamics and spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Rabitz, H.

    1991-01-01

    This research is concerned with the development and application of advanced analysis tools for studying dynamics, kinetics, and spectroscopic phenomena from a forward and inverse perspective. In particular, the forward problem is concerned with understanding how detailed interatomic potential information maps onto a hierarchy of chemical dynamic and kinetic observables. The inverse aspects of the research are concerned with exactly the reverse of this process, whereby we desire to understand how particular measurements project back to yield information regarding the potential surface. Thus, in the latter domain, our research is concerned with the development of theoretically based tools ultimately aimed at applications to the inversion of quality laboratory data for the extraction of microscopic potential information.

  14. Learning to Laugh at Ourselves: Humor, Self-Transcendence, and the Cultivation of Moral Virtues

    Science.gov (United States)

    Gordon, Mordechai

    2010-01-01

    In this essay Mordechai Gordon begins to address the neglect of humor among philosophers of education by focusing on some interesting connections between humor, self-transcendence, and the development of moral virtues. More specifically, he explores the kind of humor that makes fun of oneself and how it can affect educational encounters. Gordon…

  15. Selective Amnesia and Racial Transcendence in News Coverage of President Obama's Inauguration

    Science.gov (United States)

    Hoerl, Kristen

    2012-01-01

    The mainstream press frequently characterized the election of President Barack Obama, the first African American US President, as the realization of Martin Luther King's dream, thus crafting a postracial narrative of national transcendence. I argue that this routine characterization of Obama's election functions as a site for the production of…

  16. Boring but important: a self-transcendent purpose for learning fosters academic self-regulation.

    Science.gov (United States)

    Yeager, David S; Henderson, Marlone D; Paunesku, David; Walton, Gregory M; D'Mello, Sidney; Spitzer, Brian J; Duckworth, Angela Lee

    2014-10-01

    Many important learning tasks feel uninteresting and tedious to learners. This research proposed that promoting a prosocial, self-transcendent purpose could improve academic self-regulation on such tasks. This proposal was supported in 4 studies with over 2,000 adolescents and young adults. Study 1 documented a correlation between a self-transcendent purpose for learning and self-reported trait measures of academic self-regulation. Those with more of a purpose for learning also persisted longer on a boring task rather than giving in to a tempting alternative and, many months later, were less likely to drop out of college. Study 2 addressed causality. It showed that a brief, one-time psychological intervention promoting a self-transcendent purpose for learning could improve high school science and math grade point average (GPA) over several months. Studies 3 and 4 were short-term experiments that explored possible mechanisms. They showed that the self-transcendent purpose manipulation could increase deeper learning behavior on tedious test review materials (Study 3), and sustain self-regulation over the course of an increasingly boring task (Study 4). More self-oriented motives for learning--such as the desire to have an interesting or enjoyable career--did not, on their own, consistently produce these benefits (Studies 1 and 4).

  17. Transcending Difference: The Place of the Classics in the Curriculum of the '90s.

    Science.gov (United States)

    Dixon, James G., III

    A close examination of the classics of western civilization reveals values that transcend any narrow definition and so absolve the classical tradition from the accusations leveled against it for being mere "representations" of the dominant culture. The classical tradition, with its values of individualism, freedom, and human dignity, has…

  18. Computational Characterization of Transient Strain-Transcending Immunity against Influenza A

    Science.gov (United States)

    Farrow, David C.; Burke, Donald S.; Rosenfeld, Roni

    2015-01-01

    The enigmatic observation that the rapidly evolving influenza A (H3N2) virus exhibits, at any given time, a limited standing genetic diversity has been an impetus for much research. One of the first generative computational models to successfully recapitulate this pattern of consistently constrained diversity posits the existence of a strong and short-lived strain-transcending immunity. Building on that model, we explored a much broader set of scenarios (parameterizations) of a transient strain-transcending immunity, ran long-term simulations of each such scenario, and assessed its plausibility with respect to a set of known or estimated influenza empirical measures. We evaluated simulated outcomes using a variety of measures, both epidemiological (annual attack rate, epidemic duration, reproductive number, and peak weekly incidence), and evolutionary (pairwise antigenic diversity, fixation rate, most recent common ancestor, and kappa, which quantifies the potential for antigenic evolution). Taking cumulative support from all these measures, we show which parameterizations of strain-transcending immunity are plausible with respect to the set of empirically derived target values. We conclude that strain-transcending immunity which is milder and longer lasting than previously suggested is more congruent with the observed short- and long-term behavior of influenza. PMID:25933195

  19. Boring but Important: A Self-Transcendent Purpose for Learning Fosters Academic Self-Regulation

    Science.gov (United States)

    Yeager, David S.; Henderson, Marlone D.; D’Mello, Sidney; Paunesku, David; Walton, Gregory M.; Spitzer, Brian J.; Duckworth, Angela Lee

    2015-01-01

    Many important learning tasks feel uninteresting and tedious to learners. This research proposed that promoting a prosocial, self-transcendent purpose could improve academic self-regulation on such tasks. This proposal was supported in four studies with over 2,000 adolescents and young adults. Study 1 documented a correlation between a self-transcendent purpose for learning and self-reported trait measures of academic self-regulation. Those with more of a purpose for learning also persisted longer on a boring task rather than giving in to a tempting alternative, and, many months later, were less likely to drop out of college. Study 2 addressed causality. It showed that a brief, one-time psychological intervention promoting a self-transcendent purpose for learning could improve high school science and math GPA over several months. Studies 3 and 4 were short-term experiments that explored possible mechanisms. They showed that the self-transcendent purpose manipulation could increase deeper learning behavior on tedious test review materials (Study 3), and sustain self-regulation over the course of an increasingly-boring task (Study 4). More self-oriented motives for learning—such as the desire to have an interesting or enjoyable career—did not, on their own, consistently produce these benefits (Studies 1 and 4). PMID:25222648

  20. Bearing and Transcending Suffering with Nature and the World: A Humanistic Account

    Science.gov (United States)

    Hong Chen, Rosa

    2011-01-01

    To conceptualise moral education as "living and learning to bear suffering" offers a humanistic vision for choices people make in the face of drastic threats to their existence. This essay proposes that bearing and transcending suffering--part of the human narrative--helps human beings to realise their ethical potential. Grounded in…

  1. Self-transcendence and Eros: The human condition between desire and the infinite

    Directory of Open Access Journals (Sweden)

    Cornel W. du Toit

    2011-03-01

    Full Text Available This article treats self-transcendence – like all transcendence – as a fact of human life. Inter alia this means that the human mind perforce operates in terms of binary concepts such as finitude–infinity, inner world–outside world, self–other, desire–fulfilment, separation–union and the like. We find these concepts in most myths of origin. The concept of desire (Eros, combining unfulfilment and the infinite, particularly epitomises self-transcendence. Ralph Waldo Emerson is cited as a precursor of the mid-19th century transcendentalists, whose ideas are resurfacing in present-day secular spirituality. In this article, we examined desire in the Christian conception of the Fall as envisioned by the Jewish philosopher Martin Buber and by Hegel, who integrates mind and nature in his philosophy of Spirit. The works of Emmanuel Levinas and Paul Ricoeur are used as points of reference to help us understand self and other in a framework of self-transcendence. The impact of these ideas on a postmetaphysical epistemology was also explored. Affectivity is a neglected area in Western thought and displays the same infinitude as rationality. The article concluded with present-day strategies of self-construction in a techno-scientific consumer culture.

  2. Learning to Laugh at Ourselves: Humor, Self-Transcendence, and the Cultivation of Moral Virtues

    Science.gov (United States)

    Gordon, Mordechai

    2010-01-01

    In this essay Mordechai Gordon begins to address the neglect of humor among philosophers of education by focusing on some interesting connections between humor, self-transcendence, and the development of moral virtues. More specifically, he explores the kind of humor that makes fun of oneself and how it can affect educational encounters. Gordon…

  3. CHEMICALS

    CERN Document Server

    Medical Service

    2002-01-01

    It is reminded that all persons who use chemicals must inform CERN's Chemistry Service (TIS-GS-GC) and the CERN Medical Service (TIS-ME). Information concerning their toxicity or other hazards as well as the necessary individual and collective protection measures will be provided by these two services. Users must be in possession of a material safety data sheet (MSDS) for each chemical used. These can be obtained by one of several means : the manufacturer of the chemical (legally obliged to supply an MSDS for each chemical delivered) ; CERN's Chemistry Service of the General Safety Group of TIS ; for chemicals and gases available in the CERN Stores the MSDS has been made available via EDH either in pdf format or else via a link to the supplier's web site. Training courses in chemical safety are available for registration via HR-TD. CERN Medical Service : TIS-ME :73186 or service.medical@cern.ch Chemistry Service : TIS-GS-GC : 78546

  4. Transcendence, historicity and temporality of being elderly: nursing reflection-using Heidegger.

    Science.gov (United States)

    Guerrero-Castañeda, Raúl Fernando; Prado, Marta Lenise do; Kempfer, Silvana Silveira; Vargas, Maria Guadalupe Ojeda

    2017-01-01

    The objective is to reflect on historicity and temporality as paths for the transcendence of being elderly, based on the phenomenological concepts of Martin Heiddeger. A review of the concepts of transcendence, historicity and temporality was carried out in the work of Martín Heidegger, integrating them in the perspective of nursing for the elderly. The transcendence of the elderly adult is feasible by accessing the temporality of self in the path of its historicity to arrive at the understanding of itself that he has achieved: transcending, which is but a process of the Being itself. Being is time in itself existing in the world, existence given by the encounter of the past (to have been), present and future (becoming), the same encounter that determines the historicity of the Being. The encounter has been consummated and the Being is transcendence, with the understanding of the Being itself as a supreme point. RESUMEN El objetivo es reflexionar en la historicidad y temporalidad como caminos para la trascendencia del ser adulto mayor, basado en los conceptos fenomenológicos de Martín Heiddeger. Se llevó a cabo una revisión de los conceptos de trascendencia, historicidad y temporalidad en la obra de Martín Heidegger, realizando su integración en la perspectiva de enfermería al adulto mayor. La trascendencia del ser adulto mayor es factible accediendo a la temporalidad del mismo en el camino de su historicidad para llegar a la comprensión de sí a la que ha llegado: trascendiendo, que no es sino un proceso del mismo ser. El ser es el tiempo en sí mismo existiendo en el mundo, existencia dada por el encuentro del pasado (haber sido), presente y futuro (devenir), mismo encuentro que determina la historicidad del ser. El encuentro se ha consumado y el ser es trascendencia, como punto supremo la comprensión del ser mismo.

  5. Dynamics and Kinetics Study of "In-Water" Chemical Reactions by Enhanced Sampling of Reactive Trajectories.

    Science.gov (United States)

    Zhang, Jun; Yang, Y Isaac; Yang, Lijiang; Gao, Yi Qin

    2015-11-12

    High potential energy barriers and engagement of solvent coordinates set challenges for in silico studies of chemical reactions, and one is quite commonly limited to study reactions along predefined reaction coordinate(s). A systematic protocol, QM/MM MD simulations using enhanced sampling of reactive trajectories (ESoRT), is established to quantitatively study chemical transitions in complex systems. A number of trajectories for Claisen rearrangement in water and toluene were collected and analyzed, respectively. Evidence was found that the bond making and breaking during this reaction are concerted processes in solutions, preferentially through a chairlike configuration. Water plays an important dynamic role that helps stabilize the transition sate, and the dipole-dipole interaction between water and the solute also lowers the transition barrier. The calculated rate coefficient is consistent with the experimental measurement. Compared with water, the reaction pathway in toluene is "narrower" and the reaction rate is slower by almost three orders of magnitude due to the absence of proper interactions to stabilize the transition state. This study suggests that the "in-water" nature of the Claisen rearrangement in aqueous solution influences its thermodynamics, kinetics, as well as dynamics.

  6. Microchannel-induced change of chemical wave propagation dynamics: importance of ratio between the inlet and the channel sizes.

    Science.gov (United States)

    Nabika, Hideki; Sato, Mami; Unoura, Kei

    2013-01-07

    The ability to control chemical wave propagation dynamics could stimulate the science and technology of artificial and biological spatiotemporal oscillating phenomena. In contrast to the conventional chemical approaches to control the wave front dynamics, here we report a physical approach to tune the propagation dynamics under the same chemical conditions. By using well-designed microchannels with different channel widths and depths, the propagation velocity was successfully controlled based on two independent effects: (i) a transition in the proton diffusion mode and (ii) the formation of a slanted wave front. Numerical analysis yielded a simple relationship between the propagation velocity and the microchannel configuration, which offers a simple and general way of controlling chemical wave propagation.

  7. Programming chemical kinetics: engineering dynamic reaction networks with DNA strand displacement

    Science.gov (United States)

    Srinivas, Niranjan

    Over the last century, the silicon revolution has enabled us to build faster, smaller and more sophisticated computers. Today, these computers control phones, cars, satellites, assembly lines, and other electromechanical devices. Just as electrical wiring controls electromechanical devices, living organisms employ "chemical wiring" to make decisions about their environment and control physical processes. Currently, the big difference between these two substrates is that while we have the abstractions, design principles, verification and fabrication techniques in place for programming with silicon, we have no comparable understanding or expertise for programming chemistry. In this thesis we take a small step towards the goal of learning how to systematically engineer prescribed non-equilibrium dynamical behaviors in chemical systems. We use the formalism of chemical reaction networks (CRNs), combined with mass-action kinetics, as our programming language for specifying dynamical behaviors. Leveraging the tools of nucleic acid nanotechnology (introduced in Chapter 1), we employ synthetic DNA molecules as our molecular architecture and toehold-mediated DNA strand displacement as our reaction primitive. Abstraction, modular design and systematic fabrication can work only with well-understood and quantitatively characterized tools. Therefore, we embark on a detailed study of the "device physics" of DNA strand displacement (Chapter 2). We present a unified view of strand displacement biophysics and kinetics by studying the process at multiple levels of detail, using an intuitive model of a random walk on a 1-dimensional energy landscape, a secondary structure kinetics model with single base-pair steps, and a coarse-grained molecular model that incorporates three-dimensional geometric and steric effects. Further, we experimentally investigate the thermodynamics of three-way branch migration. Our findings are consistent with previously measured or inferred rates for

  8. Computational Cellular Dynamics Based on the Chemical Master Equation: A Challenge for Understanding Complexity.

    Science.gov (United States)

    Liang, Jie; Qian, Hong

    2010-01-01

    Modern molecular biology has always been a great source of inspiration for computational science. Half a century ago, the challenge from understanding macromolecular dynamics has led the way for computations to be part of the tool set to study molecular biology. Twenty-five years ago, the demand from genome science has inspired an entire generation of computer scientists with an interest in discrete mathematics to join the field that is now called bioinformatics. In this paper, we shall lay out a new mathematical theory for dynamics of biochemical reaction systems in a small volume (i.e., mesoscopic) in terms of a stochastic, discrete-state continuous-time formulation, called the chemical master equation (CME). Similar to the wavefunction in quantum mechanics, the dynamically changing probability landscape associated with the state space provides a fundamental characterization of the biochemical reaction system. The stochastic trajectories of the dynamics are best known through the simulations using the Gillespie algorithm. In contrast to the Metropolis algorithm, this Monte Carlo sampling technique does not follow a process with detailed balance. We shall show several examples how CMEs are used to model cellular biochemical systems. We shall also illustrate the computational challenges involved: multiscale phenomena, the interplay between stochasticity and nonlinearity, and how macroscopic determinism arises from mesoscopic dynamics. We point out recent advances in computing solutions to the CME, including exact solution of the steady state landscape and stochastic differential equations that offer alternatives to the Gilespie algorithm. We argue that the CME is an ideal system from which one can learn to understand "complex behavior" and complexity theory, and from which important biological insight can be gained.

  9. Motif analysis for small-number effects in chemical reaction dynamics

    Science.gov (United States)

    Saito, Nen; Sughiyama, Yuki; Kaneko, Kunihiko

    2016-09-01

    The number of molecules involved in a cell or subcellular structure is sometimes rather small. In this situation, ordinary macroscopic-level fluctuations can be overwhelmed by non-negligible large fluctuations, which results in drastic changes in chemical-reaction dynamics and statistics compared to those observed under a macroscopic system (i.e., with a large number of molecules). In order to understand how salient changes emerge from fluctuations in molecular number, we here quantitatively define small-number effect by focusing on a "mesoscopic" level, in which the concentration distribution is distinguishable both from micro- and macroscopic ones and propose a criterion for determining whether or not such an effect can emerge in a given chemical reaction network. Using the proposed criterion, we systematically derive a list of motifs of chemical reaction networks that can show small-number effects, which includes motifs showing emergence of the power law and the bimodal distribution observable in a mesoscopic regime with respect to molecule number. The list of motifs provided herein is helpful in the search for candidates of biochemical reactions with a small-number effect for possible biological functions, as well as for designing a reaction system whose behavior can change drastically depending on molecule number, rather than concentration.

  10. Motif analysis for small-number effects in chemical reaction dynamics.

    Science.gov (United States)

    Saito, Nen; Sughiyama, Yuki; Kaneko, Kunihiko

    2016-09-07

    The number of molecules involved in a cell or subcellular structure is sometimes rather small. In this situation, ordinary macroscopic-level fluctuations can be overwhelmed by non-negligible large fluctuations, which results in drastic changes in chemical-reaction dynamics and statistics compared to those observed under a macroscopic system (i.e., with a large number of molecules). In order to understand how salient changes emerge from fluctuations in molecular number, we here quantitatively define small-number effect by focusing on a "mesoscopic" level, in which the concentration distribution is distinguishable both from micro- and macroscopic ones and propose a criterion for determining whether or not such an effect can emerge in a given chemical reaction network. Using the proposed criterion, we systematically derive a list of motifs of chemical reaction networks that can show small-number effects, which includes motifs showing emergence of the power law and the bimodal distribution observable in a mesoscopic regime with respect to molecule number. The list of motifs provided herein is helpful in the search for candidates of biochemical reactions with a small-number effect for possible biological functions, as well as for designing a reaction system whose behavior can change drastically depending on molecule number, rather than concentration.

  11. The Dynamical and Chemical Evolution of Dwarf Spheroidal Galaxies with GEAR

    CERN Document Server

    Revaz, Yves

    2011-01-01

    We present a fully parallel chemo-dynamical Tree/SPH code, GEAR, which allows to perform high resolution simulations with detailed chemical diagnostics. Starting from the public version of Gadget-2, we included the complex treatment of the baryon physics: gas cooling, star formation law, chemical evolution and supernovae feedback. We qualified the performances of GEAR with the case of dSph galaxies. GEAR conserves the total energy budget of the systems to better than 5% over 14Gyr and proved excellent convergence of the results with numerical resolution. We showed that models of dSphs in a static Euclidean space, where the expansion of the universe is neglected are valid. In addition, we tackled some of the existing open questions in the field, like the stellar mass fraction of dSphs and its link with the predicted dark matter halo mass function, the effect of the supernova feedback, the spatial distribution of the stellar populations, and the origin of the diversity in star formation histories and chemical a...

  12. An infrared free-electron laser for the Chemical Dynamics Research Laboratory. Design report

    Energy Technology Data Exchange (ETDEWEB)

    Vaughan, D. [comp.

    1992-04-01

    This document describes a free-electron laser (FEL) proposed as part of the Chemical Dynamics Research Laboratory (CDRL), a user facility that also incorporates several advanced lasers of conventional design and two beamlines for the ALS. The FEL itself addresses the needs of the chemical sciences community for a high-brightness, tunable source covering a broad region of the infrared spectrum -- from 3 to 50 {mu}m. All of these sources, together with a variety of sophisticated experimental stations, will be housed in a new building to be located adjacent to the ALS. The radiation sources can be synchronized to permit powerful two-color, pump-probe experiments that will further our fundamental understanding of chemical dynamics at the molecular level, especially those aspects relevant to practical issues in combustion chemistry. The technical approach adopted in this design makes use of superconducting radiofrequency (SCRF) accelerating structures. The primary motivation for adopting this approach was to meet the user requirement for wavelength stability equal to one part in 10{sup 4}. Previous studies concluded that a wavelength stability of only one part in 10{sup 3} could be achieved with currently available room-temperature technology. In addition, the superconducting design operates in a continuous-wave (cw) mode and hence offers considerably higher average optical output power. It also allows for various pulse-gating configurations that will permit simultaneous multiuser operations. A summary of the comparative performance attainable with room-temperature and superconducting designs is given. The FEL described in this report provides a continuous train of 30-ps micropulses, with 100{mu}J of optical energy per micropulse, at a repetition rate of 6.1 MHz. The device can also deliver pulses at a cw repetition rate of 12.2 MHz, with a peak power of 50 {mu}J per micropulse. 70 ref.

  13. An infrared free-electron laser for the Chemical Dynamics Research Laboratory

    Energy Technology Data Exchange (ETDEWEB)

    Vaughan, D. (comp.)

    1992-04-01

    This document describes a free-electron laser (FEL) proposed as part of the Chemical Dynamics Research Laboratory (CDRL), a user facility that also incorporates several advanced lasers of conventional design and two beamlines for the ALS. The FEL itself addresses the needs of the chemical sciences community for a high-brightness, tunable source covering a broad region of the infrared spectrum -- from 3 to 50 {mu}m. All of these sources, together with a variety of sophisticated experimental stations, will be housed in a new building to be located adjacent to the ALS. The radiation sources can be synchronized to permit powerful two-color, pump-probe experiments that will further our fundamental understanding of chemical dynamics at the molecular level, especially those aspects relevant to practical issues in combustion chemistry. The technical approach adopted in this design makes use of superconducting radiofrequency (SCRF) accelerating structures. The primary motivation for adopting this approach was to meet the user requirement for wavelength stability equal to one part in 10{sup 4}. Previous studies concluded that a wavelength stability of only one part in 10{sup 3} could be achieved with currently available room-temperature technology. In addition, the superconducting design operates in a continuous-wave (cw) mode and hence offers considerably higher average optical output power. It also allows for various pulse-gating configurations that will permit simultaneous multiuser operations. A summary of the comparative performance attainable with room-temperature and superconducting designs is given. The FEL described in this report provides a continuous train of 30-ps micropulses, with 100{mu}J of optical energy per micropulse, at a repetition rate of 6.1 MHz. The device can also deliver pulses at a cw repetition rate of 12.2 MHz, with a peak power of 50 {mu}J per micropulse. 70 ref.

  14. Amoeba-Inspired Heuristic Search Dynamics for Exploring Chemical Reaction Paths.

    Science.gov (United States)

    Aono, Masashi; Wakabayashi, Masamitsu

    2015-09-01

    We propose a nature-inspired model for simulating chemical reactions in a computationally resource-saving manner. The model was developed by extending our previously proposed heuristic search algorithm, called "AmoebaSAT [Aono et al. 2013]," which was inspired by the spatiotemporal dynamics of a single-celled amoeboid organism that exhibits sophisticated computing capabilities in adapting to its environment efficiently [Zhu et al. 2013]. AmoebaSAT is used for solving an NP-complete combinatorial optimization problem [Garey and Johnson 1979], "the satisfiability problem," and finds a constraint-satisfying solution at a speed that is dramatically faster than one of the conventionally known fastest stochastic local search methods [Iwama and Tamaki 2004] for a class of randomly generated problem instances [ http://www.cs.ubc.ca/~hoos/5/benchm.html ]. In cases where the problem has more than one solution, AmoebaSAT exhibits dynamic transition behavior among a variety of the solutions. Inheriting these features of AmoebaSAT, we formulate "AmoebaChem," which explores a variety of metastable molecules in which several constraints determined by input atoms are satisfied and generates dynamic transition processes among the metastable molecules. AmoebaChem and its developed forms will be applied to the study of the origins of life, to discover reaction paths for which expected or unexpected organic compounds may be formed via unknown unstable intermediates and to estimate the likelihood of each of the discovered paths.

  15. Reaction mechanisms of aqueous monoethanolamine with carbon dioxide: a combined quantum chemical and molecular dynamics study.

    Science.gov (United States)

    Hwang, Gyeong S; Stowe, Haley M; Paek, Eunsu; Manogaran, Dhivya

    2015-01-14

    Aqueous monoethanolamine (MEA) has been extensively studied as a solvent for CO2 capture, yet the underlying reaction mechanisms are still not fully understood. Combined ab initio and classical molecular dynamics simulations were performed to revisit and identify key elementary reactions and intermediates in 25-30 wt% aqueous MEA with CO2, by explicitly taking into account the structural and dynamic effects. Using static quantum chemical calculations, we also analyzed in more detail the fundamental interactions involved in the MEA-CO2 reaction. We find that both the CO2 capture by MEA and solvent regeneration follow a zwitterion-mediated two-step mechanism; from the zwitterionic intermediate, the relative probability between deprotonation (carbamate formation) and CO2 removal (MEA regeneration) tends to be determined largely by the interaction between the zwitterion and neighboring H2O molecules. In addition, our calculations clearly demonstrate that proton transfer in the MEA-CO2-H2O solution primarily occurs through H-bonded water bridges, and thus the availability and arrangement of H2O molecules also directly impacts the protonation and/or deprotonation of MEA and its derivatives. This improved understanding should contribute to developing more comprehensive kinetic models for use in modeling and optimizing the CO2 capture process. Moreover, this work highlights the importance of a detailed atomic-level description of the solution structure and dynamics in order to better understand molecular mechanisms underlying the reaction of CO2 with aqueous amines.

  16. Amoeba-Inspired Heuristic Search Dynamics for Exploring Chemical Reaction Paths

    Science.gov (United States)

    Aono, Masashi; Wakabayashi, Masamitsu

    2015-09-01

    We propose a nature-inspired model for simulating chemical reactions in a computationally resource-saving manner. The model was developed by extending our previously proposed heuristic search algorithm, called "AmoebaSAT [Aono et al. 2013]," which was inspired by the spatiotemporal dynamics of a single-celled amoeboid organism that exhibits sophisticated computing capabilities in adapting to its environment efficiently [Zhu et al. 2013]. AmoebaSAT is used for solving an NP-complete combinatorial optimization problem [Garey and Johnson 1979], "the satisfiability problem," and finds a constraint-satisfying solution at a speed that is dramatically faster than one of the conventionally known fastest stochastic local search methods [Iwama and Tamaki 2004] for a class of randomly generated problem instances [http://www.cs.ubc.ca/~hoos/5/benchm.html]. In cases where the problem has more than one solution, AmoebaSAT exhibits dynamic transition behavior among a variety of the solutions. Inheriting these features of AmoebaSAT, we formulate "AmoebaChem," which explores a variety of metastable molecules in which several constraints determined by input atoms are satisfied and generates dynamic transition processes among the metastable molecules. AmoebaChem and its developed forms will be applied to the study of the origins of life, to discover reaction paths for which expected or unexpected organic compounds may be formed via unknown unstable intermediates and to estimate the likelihood of each of the discovered paths.

  17. Chemical Ligation and Isotope Labeling to Locate Dynamic Effects during Catalysis by Dihydrofolate Reductase.

    Science.gov (United States)

    Luk, Louis Y P; Ruiz-Pernía, J Javier; Adesina, Aduragbemi S; Loveridge, E Joel; Tuñón, Iñaki; Moliner, Vincent; Allemann, Rudolf K

    2015-07-27

    Chemical ligation has been used to alter motions in specific regions of dihydrofolate reductase from E. coli and to investigate the effects of localized motional changes on enzyme catalysis. Two isotopic hybrids were prepared; one with the mobile N-terminal segment containing heavy isotopes ((2) H, (13) C, (15) N) and the remainder of the protein with natural isotopic abundance, and the other one with only the C-terminal segment isotopically labeled. Kinetic investigations indicated that isotopic substitution of the N-terminal segment affected only a physical step of catalysis, whereas the enzyme chemistry was affected by protein motions from the C-terminal segment. QM/MM studies support the idea that dynamic effects on catalysis mostly originate from the C-terminal segment. The use of isotope hybrids provides insights into the microscopic mechanism of dynamic coupling, which is difficult to obtain with other studies, and helps define the dynamic networks of intramolecular interactions central to enzyme catalysis.

  18. Vulnerability to alcohol consumption, spiritual transcendence and psychosocial well-being: test of a theory.

    Science.gov (United States)

    Heredia, Luz Patricia Díaz; Sanchez, Alba Idaly Muñoz

    2016-06-07

    to demonstrate the relations among vulnerability, self-transcendence and well-being in the young adult population and the effect of each of these variables on the adoption of low-risk consumption conducts. quantitative and cross-sectional correlation study using structural equations analysis to test the relation among the variables. an inverse relation was evidenced between vulnerability to alcohol consumption and spiritual transcendence (β-0.123, p 0.025) and a direct positive relation between spiritual transcendence and psychosocial well-being (β 0.482, p 0.000). the relations among the variables spiritual transcendence, vulnerability to alcohol consumption and psychosocial well-being, based on Reed's Theory, are confirmed in the population group of young college students, concluding that psychosocial well-being can be achieved when spiritual transcendence is enhanced, as the vulnerability to alcohol consumption drops. demonstrar as relações entre vulnerabilidade, autotranscendência e bem-estar na população adulta jovem e o efeito de cada uma destas variáveis na adoção de condutas de baixo risco de consumo. estudo quantitativo, transversal do tipo correlacional que utilizou a análise estatística de Equações Estruturais para comprovar a relação entre as variáveis. evidenciou-se uma relação inversa entre a vulnerabilidade ao consumo do álcool e a transcendência espiritual (β-0.123, p 0.025) e uma relação direta positiva entre a transcendência espiritual e o bem-estar psicossocial (β 0.482, p 0.000). Conclusões: as relações das variáveis transcendência espiritual, vulnerabilidade ao consumo do álcool e bem-estar psicossocial, fundamentadas na Teoria de Reed, são confirmadas no grupo populacional de jovens adultos universitários, concluindo que é possível alcançar o bem-estar psicossocial quando se incrementa a transcendência espiritual, enquanto a vulnerabilidade ao consumo do álcool se reduz. demostrar las relaciones entre

  19. Synchronization dynamics of chemically coupled cells with activator–inhibitor pathways

    Energy Technology Data Exchange (ETDEWEB)

    Guemkam Ghomsi, P. [Complex Systems and Theoretical Biology Group, Laboratory of Research on Advanced Materials and Nonlinear Science (LaRAMaNS), Department of Physics, Faculty of Science, University of Buea, P.O. Box 63, Buea (Cameroon); Laboratoire de Mécanique, Department of Physics, Faculty of Science, University of Yaoundé I, P.O. Box 812, Yaoundé (Cameroon); Moukam Kakmeni, F.M., E-mail: moukam.kakmeni@ubuea.cm [Complex Systems and Theoretical Biology Group, Laboratory of Research on Advanced Materials and Nonlinear Science (LaRAMaNS), Department of Physics, Faculty of Science, University of Buea, P.O. Box 63, Buea (Cameroon); Kofane, T.C.; Tchawoua, C. [Laboratoire de Mécanique, Department of Physics, Faculty of Science, University of Yaoundé I, P.O. Box 812, Yaoundé (Cameroon)

    2014-08-01

    Systems of interacting cells containing an activator–inhibitor pathway, regulating naturally in their inner parts their end-product concentrations through a sequence of biochemical reactions with feedback-loops: an end-product inhibition of the first substrate, and an autocatalytic activation of the end-product through an allosteric enzyme-mediated reaction are investigated. The individual cells are considered to be identical and are described by nonlinear differential equations recently proposed following the concerted transition model. The chemical and electrical coupling types, realized by exchange of metabolites across concentration of the cells are used in order to analyze the onset of phase and complete synchronization in the biochemical system. It is found that depending on the coupling nature and the range of coupling strength, cells enter into different synchronization regimes going from low-quality to high-quality synchronization. The synchronization manifold's stability is analyzed. The results are supported by numerical simulations using indicators such as the conditional Lyapunov exponents and the rate of change of the Lyapunov function. The results indicate that the system cannot completely synchronize under the single action of the chemical coupling. The combined effect of both chemical and electrical couplings is found to be of capital importance in the onset of complete synchronization and high quality synchronization. - Highlights: • We investigate the dynamics and synchronization of cells with activator–inhibitor pathways. • A complete study of fixed points' stability and bifurcations of the system is done. • It is found that chemically coupled cells only display phase synchronization. • Electrical coupling is important for complete synchronization in the coupled cells. • High quality synchronization is observed in the coupled cells.

  20. The dynamic behavior of a liquid ethanol-water mixture: a perspective from quantum chemical topology.

    Science.gov (United States)

    Mejía, Sol M; Mills, Matthew J L; Shaik, Majeed S; Mondragon, Fanor; Popelier, Paul L A

    2011-05-07

    Quantum Chemical Topology (QCT) is used to reveal the dynamics of atom-atom interactions in a liquid. A molecular dynamics simulation was carried out on an ethanol-water liquid mixture at its azeotropic concentration (X(ethanol)=0.899), using high-rank multipolar electrostatics. A thousand (ethanol)(9)-water heterodecamers, respecting the water-ethanol ratio of the azeotropic mixture, were extracted from the simulation. Ab initio electron densities were computed at the B3LYP/6-31+G(d) level for these molecular clusters. A video shows the dynamical behavior of a pattern of bond critical points and atomic interaction lines, fluctuating over 1 ns. A bond critical point distribution revealed the fluctuating behavior of water and ethanol molecules in terms of O-H···O, C-H···O and H···H interactions. Interestingly, the water molecule formed one to six C-H···O and one to four O-H···O interactions as a proton acceptor. We found that the more localized a dynamical bond critical point distribution, the higher the average electron density at its bond critical points. The formation of multiple C-H···O interactions affected the shape of the oxygen basin of the water molecule, which is shown in three dimensions. The hydrogen atoms of water strongly preferred to form H···H interactions with ethanol's alkyl hydrogen atoms over its hydroxyl hydrogen. This journal is © the Owner Societies 2011

  1. ThermoData engine (TDE): software implementation of the dynamic data evaluation concept. 4. Chemical reactions.

    Science.gov (United States)

    Diky, Vladimir; Chirico, Robert D; Kazakov, Andrei F; Muzny, Chris D; Frenkel, Michael

    2009-12-01

    ThermoData Engine (TDE) is the first full-scale software implementation of the dynamic data evaluation concept, as reported recently in this journal. This paper describes the first application of this concept to the evaluation of thermodynamic properties for chemical reactions. Reaction properties evaluated are the enthalpies, entropies, Gibbs energies, and thermodynamic equilibrium constants. Details of key considerations in the critical evaluation of enthalpies of formation and of standard entropies for organic compounds are discussed in relation to their application in the calculation of reaction properties. Extensions to the class structure of the program are described that allow close linkage between the derived reaction properties and the underlying pure-component properties. Derivation of pure-component enthalpies of formation and of standard entropies through the use of directly measured reaction properties (enthalpies of reaction and equilibrium constants) is described. Directions for future enhancements are outlined.

  2. Dynamics of wicking in silicon nanopillars fabricated with interference lithography and metal-assisted chemical etching.

    Science.gov (United States)

    Mai, Trong Thi; Lai, Chang Quan; Zheng, H; Balasubramanian, Karthik; Leong, K C; Lee, P S; Lee, Chengkuo; Choi, W K

    2012-08-07

    The capillary rise of liquid on a surface, or "wicking", has potential applications in biological and industrial processes such as drug delivery, oil recovery, and integrated circuit chip cooling. This paper presents a theoretical study on the dynamics of wicking on silicon nanopillars based on a balance between the driving capillary forces and viscous dissipation forces. Our model predicts that the invasion of the liquid front follows a diffusion process and strongly depends on the structural geometry. The model is validated against experimental observations of wicking in silicon nanopillars with different heights synthesized by interference lithography and metal-assisted chemical etching techniques. Excellent agreement between theoretical and experimental results, from both our samples and data published in the literature, was achieved.

  3. Chemical and dynamical impacts of stratospheric sudden warmings on Arctic ozone variability

    Science.gov (United States)

    Strahan, S. E.; Douglass, A. R.; Steenrod, S. D.

    2016-10-01

    We use the Global Modeling Initiative (GMI) chemistry and transport model with Modern-Era Retrospective Analysis for Research and Applications (MERRA) meteorological fields to quantify heterogeneous chemical ozone loss in Arctic winters 2005-2015. Comparisons to Aura Microwave Limb Sounder N2O and O3 observations show the GMI simulation credibly represents the transport processes and net heterogeneous chemical loss necessary to simulate Arctic ozone. We find that the maximum seasonal ozone depletion varies linearly with the number of cold days and with wave driving (eddy heat flux) calculated from MERRA fields. We use this relationship and MERRA temperatures to estimate seasonal ozone loss from 1993 to 2004 when inorganic chlorine levels were in the same range as during the Aura period. Using these loss estimates and the observed March mean 63-90°N column O3, we quantify the sensitivity of the ozone dynamical resupply to wave driving, separating it from the sensitivity of ozone depletion to wave driving. The results show that about 2/3 of the deviation of the observed March Arctic O3 from an assumed climatological mean is due to variations in O3 resupply and 1/3 is due to depletion. Winters with a stratospheric sudden warming (SSW) before mid-February have about 1/3 the depletion of winters without one and export less depletion to the midlatitudes. However, a larger effect on the spring midlatitude ozone comes from dynamical differences between warm and cold Arctic winters, which can mask or add to the impact of exported depletion.

  4. OBLIQUE WAYS OF TRANSCENDENCE: ASPECTS OF IDEALISM IN AUGUSTO DOS ANJOS AND PEDRO KILKERRY

    Directory of Open Access Journals (Sweden)

    Fabiano Rodrigo da Silva Santos

    2015-07-01

    Full Text Available This essay analyzes the manifestations of the idealism of romantic orientation in the poetry of Augusto dos Anjos and Pedro Kilkerry, showing the points of contact between their oeuvres and demonstrating that many of the innovative aesthetic procedures of their poetry appear as a reaction to urgencies of an idealistic conception of poetry. Augusto dos Anjos and Pedro Kilkerry attest the anxiety of apprehension of connections with a super-sensible sphere in phenomenal reality. Although this takes a different form in each of the poets, it can refer to a common poetic ideal that transcends the concrete reality. To accomplish this, they use aesthetic procedures that modernize the language of the romantic sublime – Augusto dos Anjos uses a hybrid philosophical repertoire that marks his poetry with a tense and innovative prosaic language, and Pedro Kilkerry opts for the indirect representation, made by an evocative and metonymic language, that evidences the mystery of the transcendent ideal without deciphering it.

  5. On the convergence of complex Langevin dynamics: the three-dimensional XY model at finite chemical potential

    CERN Document Server

    Aarts, Gert

    2010-01-01

    The three-dimensional XY model is studied at finite chemical potential using complex Langevin dynamics. The validity of the approach is probed at small chemical potential using imaginary chemical potential and continuity arguments, and at larger chemical potential by comparison with the world line method. While complex Langevin works for larger beta, we find that it fails for smaller beta, in the region of the phase diagram corresponding to the disordered phase. Diagnostic tests are developed to identify symptoms correlated with incorrect convergence. We argue that the erroneous behaviour at smaller beta is not due to the sign problem, but rather resembles dynamics observed in complex Langevin simulations of simple models with complex noise.

  6. Chemical Control for Host-Parasitoid Model within the Parasitism Season and Its Complex Dynamics

    Directory of Open Access Journals (Sweden)

    Tao Wang

    2016-01-01

    Full Text Available In the present paper, we develop a host-parasitoid model with Holling type II functional response function and chemical control, which can be applied at any time of each parasitism season or pest generation, and focus on addressing the importance of the timing of application pesticide during the parasitism season or pest generation in successful pest control. Firstly, the existence and stability of both the host and parasitoid populations extinction equilibrium and parasitoid-free equilibrium have been investigated. Secondly, the effects of key parameters on the threshold conditions have been discussed in more detail, which shows the importance of pesticide application times on the pest control. Thirdly, the complex dynamics including multiple attractors coexistence, chaotic behavior, and initial sensitivity have been studied by using numerical bifurcation analyses. Finally, the uncertainty and sensitivity of all the parameters on the solutions of both the host and parasitoid populations are investigated, which can help us to determine the key parameters in designing the pest control strategy. The present research can help us to further understand the importance of timings of pesticide application in the pest control and to improve the classical chemical control and to make management decisions.

  7. Dissipative particle dynamics simulation of wettability alternation phenomena in the chemical flooding process

    Institute of Scientific and Technical Information of China (English)

    Xiaobo Li; Yuewu Liu; Jianfei Tang; Shujiao Li

    2009-01-01

    Wettability alternation phenomena is considered one of the most important enhanced oil recovery (EOR) mechanisms in the chemical flooding process and induced by the adsorption of surfactant on the rock surface. These phenomena are studied by a mesoscopic method named as dissipative particle dynamics (DPD). Both the alteration phenomena of water-wet to oil-wet and that of oil-wet to waterwet are simulated based on reasonable definition of interaction parameters between beads. The wetting hysteresis phenomenon and the process of oil-drops detachment from rock surfaces with different wettability are simulated by adding long-range external forces on the fluid particles. The simulation results show that, the oil drop is liable to spread on the oil-wetting surface and move in the form of liquid film flow, whereas it is likely to move as a whole on the waterwetting surface. There are the same phenomena occuring in wettability-alternated cases. The results also show that DPD method provides a feasible approach to the problems of seepage flow with physicochemical phenomena and can be used to study the mechanism of EOR of chemical flooding.

  8. Processing of proprioceptive and vestibular body signals and self-transcendence in Ashtanga yoga practitioners

    Directory of Open Access Journals (Sweden)

    Francesca eFiori

    2014-09-01

    Full Text Available In the rod and frame test (RFT, participants are asked to set a tilted visual linear marker (i.e. a rod, embedded in a square, to the subjective vertical, irrespective of the surrounding frame. People not influenced by the frame tilt are defined as field-independent, while people biased in their rod verticality perception are field-dependent. Performing RFT requires the integration of proprioceptive, vestibular and visual signals with the latter accounting for field-dependency. Studies indicate that motor experts in body-related, balance-improving disciplines tend to be field-independent, i.e. better at verticality perception, suggesting that proprioceptive and vestibular expertise acquired by such exercise may weaken the influence of irrelevant visual signals. What remains unknown is whether the effect of body-related expertise in weighting perceptual information might also be mediated by personality traits, in particular those indexing self-focusing abilities. To explore this issue, we tested field-dependency in a class of body experts, namely yoga practitioners and in non-expert participants. Moreover we explored any link between performance on RFT and self-transcendence, a complex personality construct, which refers to tendency to experience spiritual feelings and ideas. As expected, yoga practitioners (i were more accurate in assessing the rod’s verticality on the RFT, and (ii expressed significantly higher self-transcendence. Interestingly, the performance in these two tests was negatively correlated. More specifically, when asked to provide verticality judgments, highly self-transcendent yoga practitioners were significantly less influenced by a misleading visual context. Our results suggest that being highly self-transcendent may enable yoga practitioners to optimize verticality judgment tasks by relying more on internal (vestibular and proprioceptive signals coming from their own body, rather than on exteroceptive, visual cues.

  9. Bipolar Disorder and the TCI: Higher Self-Transcendence in Bipolar Disorder Compared to Major Depression

    Directory of Open Access Journals (Sweden)

    James A. Harley

    2011-01-01

    With correction for mood state, total harm avoidance (HA was higher than unaffected in both MDD and BP groups, but the mood disorder groups did not differ from each other. However, BP1 individuals had higher self-transcendence (ST than those with MDD and unaffected relatives. HA may reflect a trait marker of mood disorders whereas high ST may be specific to BP. As ST is heritable, genes that affect ST may be of relevance for vulnerability to BP.

  10. The Effect of Self-Transcendence on Depression in Cognitively Intact Nursing Home Patients

    OpenAIRE

    Gørill Haugan; Siw Tone Innstrand

    2012-01-01

    Aims. This study's aim was to test the effects of self-transcendence on depression among cognitively intact nursing home patients. Background. Depression is considered the most frequent mental disorder among the elderly population. Specifically, the depression rate among nursing home patients is three to four times higher than that among community-dwelling elderly. Therefore, finding new and alternative ways to prevent and decrease depression is of great importance for nursing home patients' ...

  11. Genitalia burn: accident or violence? Concerns that transcend injury treatment

    Directory of Open Access Journals (Sweden)

    Ana Lúcia Ferreira

    2014-06-01

    Full Text Available OBJECTIVE: To describe a case of genital burn which raised the suspicion of maltreatment (sexual abuse and neglect by lack of supervision.CASE DESCRIPTION: An infant was taken to the Emergency Room of a pediatric hospital with an extensive burn in the vulva and perineum. The mother claimed the burn had been caused by a sodium-hydroxide-based product. However, the injury severity led to the suspicion of sexual abuse, which was then ruled out by a multidisciplinary team, based on the consistent report by the mother. Besides, the lesion type matched those caused by the chemical agent involved in the accident and the family context was evaluated and considered adequate. The patient had a favorable outcome and was discharged after four days of hospitalization. Outpatient follow-up during six months after the accident enabled the team to rule out neglect by lack of supervision.COMMENTS: Accidents and violence are frequent causes of physical injuries in children, and the differential diagnosis between them can be a challenge for healthcare workers, especially in rare clinical conditions involving patients who cannot speak for themselves. The involvement of a multidisciplinary trained team helps to have an adequate approach, ensuring child protection and developing a bond with the family; the latter is essential for a continued patient follow-up.

  12. Computational modelling of the complex dynamics of chemically blown polyurethane foam

    Science.gov (United States)

    Ireka, I. E.; Niedziela, D.; Schäfer, K.; Tröltzsch, J.; Steiner, K.; Helbig, F.; Chinyoka, T.; Kroll, L.

    2015-11-01

    This study presents computational analysis of the complex dynamics observed in chemically blown polyurethane foams during reaction injection molding process. The mathematical formulation introduces an experimentally motivated non-divergence free setup for the continuity equations which reflects the self expanding behaviour observed in the physical system. The foam growth phenomena which is normally initiated by adequate pre-mixing of necessary reactant polymers, leading to an exothermic polymerization reaction, bubble nucleation, and gas formation, is captured numerically. We assume the dependence of material viscosity on the degree of cure/polymerization, gas volume fraction, and temperature as well as non-dependence of mixture density on pressure. The set of unsteady nonlinear coupled partial differential equations describing the dynamics of the system are solved numerically for state variables using finite volume techniques such that the front of the flow is tracked with high resolution interface capturing schemes. Graphical representation of the foam volume fraction, evolution of foam heights, and temperature distributions is presented. Results from our simulations are validated with experimental data. These results show good quantitative agreement with observations from experiments.

  13. Water Organization and Dynamics on Mineral Surfaces Interrogated by Graph Theoretical Analyses of Intermolecular Chemical Networks

    Directory of Open Access Journals (Sweden)

    Abdullah Ozkanlar

    2014-03-01

    Full Text Available Intermolecular chemical networks defined by the hydrogen bonds formed at the α-quartz|water interface have been data-mined using graph theoretical methods so as to identify and quantify structural patterns and dynamic behavior. Using molecular-dynamics simulations data, the hydrogen bond (H-bond distributions for the water-water and water-silanol H-bond networks have been determined followed by the calculation of the persistence of the H-bond, the dipole-angle oscillations that water makes with the surface silanol groups over time, and the contiguous H-bonded chains formed at the interface. Changes in these properties have been monitored as a function of surface coverage. Using the H-bond distribution between water and the surface silanol groups, the actual number of waters adsorbed to the surface is found to be 0.6 H2O/10 Å2, irrespective of the total concentration of waters within the system. The unbroken H-bond network of interfacial waters extends farther than in the bulk liquid; however, it is more fluxional at low surface coverages (i.e., the H-bond persistence in a monolayer of water is shorter than in the bulk Concentrations of H2O at previously determined water adsorption sites have also been quantified. This work demonstrates the complementary information that can be obtained through graph theoretical analysis of the intermolecular H-bond networks relative to standard analyses of molecular simulation data.

  14. Transport model of chemical secretion process for tracking exocytotic event dynamics using electroanalysis.

    Science.gov (United States)

    Fan, Tai-Hsi; Fedorov, Andrei G

    2004-08-01

    A unified model is developed to analyze the key features of the chemical secretion process observed in experimental studies of various vesicles with application to electroanalytical measurements of vesicular exocytosis. The intimately coupled dynamics and kinetics are simultaneously resolved based on continuum fluid flow, mass transport, and linear elasticity theories combined with biomembrane mechanics. We report three case studies of exocytosis, including a large electroporated granule of the mast cell, a small and clear synaptic vesicle, and a medium size vesicle in the chromaffin cell. The simulation results for each case are compared with electroanalytical measurements from the literature. The results provide a theoretical ground for defining the rate-controlling step(s) of an exocytotic sequence, allowing interpretation of electroanalysis data. Thus, it provides a tool for theoretical verification of competing hypotheses of what controls/limits messenger release during exocytosis. Simulations show that the pore size, the pore opening velocity, and the swelling dynamics of the granule matrix play the key roles in controlling the messenger release kinetics.

  15. Transcendent and Immanent in the Orthodox Theology. Implications and Missionary Evaluation

    Directory of Open Access Journals (Sweden)

    Gheorghe Istodor

    2016-03-01

    Full Text Available Transcendent and immanent are not valued in Orthodox Theology as simple concepts and they give sense to existence and salvation only in a personalist register. Their existence, both in the plan of eternity, as well as temporary, it is professed by the Church, and in the manner of which they relate and co-exist is the determining factor for understanding and preaching the truth of the hypostatic union in Jesus Christ, real God and real Man. The absolutization of the transcendence and immanence by philosophy or ideology is not accepted by Theology for the harmful consequences with regard to God, man and creation; also, the absolutization of these two lead to the elimination of Christ’s deity, reduced to a historical condition, marked either by the genius, or by the powerlessness and instinctuality. From missionary perspective, distortion of the relationship between transcendence and immanence leads to the intensification of the process of secularization, but also to anti- Christian phenomena such as desacralization, indifference and unchristianizing.

  16. Hahneman’s Principles Anthropology of Transcendent Philosophy : Some Observations in the Light of Islamic Sources

    Directory of Open Access Journals (Sweden)

    Hanafi Mohd. Nor

    2011-12-01

    Full Text Available This paper seeks to retrace human nature and transcending the vision of  humanity, by identifying, describing and analyzing the Hahnemannian principles and their relevance to anthropology of transcendent philosophy. Using the qualitative data from Hahnemann’s works with special reference to his Organon we found that Hahnemann’s principles are, unquestionably, a philosophical system in its own right. The primary goal of his philosophy, however is not solely speculative, indeed it is a medical philosophy written in brief  aphoristic style, aimed more of guidelines at curing suffering human beings, rather than winning adherents to its speculative creed. The main concern of  Hahnemann with regard to his medical philosophy is actually the question of suffering human well-being. The answer to this question will provide an indication of the relevant of  Hahnemannian principles to anthropology of transcendent philosophy. Thus Hahnemann’s principles cannot be properly understood apart from some grasp of  his conception of human nature and philosophy as a whole. Nonetheless his ideas are against the new emergence mainstream thought pattern of modern Europe which in turn spread all over the globe.

  17. Classical molecular dynamics and ab initio simulations of chemical-mechanical polishing of amorphous silica

    Science.gov (United States)

    Chagarov, Evgueni Anatolievich

    Chemical-mechanical polishing (CMP) is a widely accepted process in the semiconductor industry. Despite intense theoretical and experimental research on CMP, there is a serious lack of fundamental understanding of the physical-chemical processes of polishing. The present work is intended to investigate these fundamental processes on an atomistic level. To model CMP on the atomic scale, a model of the amorphous silica is prepared by applying Design of Experiments (DOE) techniques to systematically investigate molecular dynamics preparation. These simulations yield high-quality models of amorphous silica, which are in excellent agreement with experimental results and are defect-free. Molecular dynamics simulations are performed to investigate the mechanical deformation during CMP of silica for different geometries and relative velocities. The simulations clarify asperity shape evolution during the process of shear and reveal temperature distributions as a function of time. It is found that the ratio of radii of a particle and asperity strongly affects the amount of the material removed whereas the relative velocity has a weaker affect on it. During shear, a significant local temperature increase occurs. This temperature increase lasts for a short time (picoseconds), but it can have a major impact on the amount of material removed. It is found that there could be significant deposition of the material from the particle to the slab, which can fill surface trenches and thereby make the surface smoother. An analytic model is developed for describing the amount of material removed as a function of asperity and particle radii and relative velocity. Density-functional calculations of different surfaces of two silica polymorphs, alpha-quartz and beta-cristobalite, are performed. The surface energies are calculated as a function of oxygen partial pressure for several different surface reconstructions and terminations. The case of hydrogen passivation is investigated to

  18. Dynamic three-dimensional micropatterned cell co-cultures within photocurable and chemically degradable hydrogels.

    Science.gov (United States)

    Sugiura, Shinji; Cha, Jae Min; Yanagawa, Fumiki; Zorlutuna, Pinar; Bae, Hojae; Khademhosseini, Ali

    2016-08-01

    In this paper we report on the development of dynamically controlled three-dimensional (3D) micropatterned cellular co-cultures within photocurable and chemically degradable hydrogels. Specifically, we generated dynamic co-cultures of micropatterned murine embryonic stem (mES) cells with human hepatocellular carcinoma (HepG2) cells within 3D hydrogels. HepG2 cells were used due to their ability to direct the differentiation of mES cells through secreted paracrine factors. To generate dynamic co-cultures, mES cells were first encapsulated within micropatterned photocurable poly(ethylene glycol) (PEG) hydrogels. These micropatterned cell-laden PEG hydrogels were subsequently surrounded by calcium alginate (Ca-Alg) hydrogels containing HepG2 cells. After 4 days, the co-culture step was halted by exposing the system to sodium citrate solution, which removed the alginate gels and the encapsulated HepG2 cells. The encapsulated mES cells were then maintained in the resulting cultures for 16 days and cardiac differentiation was analysed. We observed that the mES cells that were exposed to HepG2 cells in the co-cultures generated cells with higher expression of cardiac genes and proteins, as well as increased spontaneous beating. Due to its ability to control the 3D microenvironment of cells in a spatially and temporally regulated manner, the method presented in this study is useful for a range of cell-culture applications related to tissue engineering and regenerative medicine. Copyright © 2013 John Wiley & Sons, Ltd.

  19. Perspective: On the relevance of slower-than-femtosecond time scales in chemical structural-dynamics studies

    Directory of Open Access Journals (Sweden)

    Philip Coppens

    2015-03-01

    Full Text Available A number of examples illustrate structural-dynamics studies of picosecond and slower photo-induced processes. They include molecular rearrangements and excitations. The information that can be obtained from such studies is discussed. The results are complementary to the information obtained from femtosecond studies. The point is made that all pertinent time scales should be covered to obtain comprehensive insight in dynamic processes of chemical and biological importance.

  20. Contents of chemical elements in stomach during prenatal development: different age-dependent dynamical changes and their significance

    Institute of Scientific and Technical Information of China (English)

    Shao-Fan Hou; Hai-Rong Li; Li-Zhen Wang; De-Zhu Li; Lin-Sheng Yang; Chong-Zheng Li

    2003-01-01

    AIM: To observe dynamic of different chemical elements in stomach tissue during fetal development.METHODS: To determine contents of the 21 chemical elements in each stomach samples from fetus aging four to ten months. The content values were compared to those from adult tissue samples, and the values for each month group were also analyzed for dynamic changes.RESULTS: Three representations were found regarding the relationship between contents of the elements and ages of the fetus, including the positive correlative (K), reversely correlative (Na, Ca, P, Al, Cu, Zn, Fe, Mn, Cr, Sr, Li, Cd, Ba,Se ) and irrelevant groups (Mg, Co, Ni, V, Pb, Ti).CONCLUSION: The chemical elements' contents in stomach tissues were found to change dynamically with the stomach weights. The age-dependent representations for different chemical elements during the prenatal development may be of some significance for assessing development of fetal stomach and some chemical elements. The data may be helpful for the nutritional balance of fetus and mothers during prenatal development and even the perinatal stages.

  1. Contents of chemical elements in stomach during prenatal development: different age-dependent dynamical changes and their significance

    Science.gov (United States)

    Hou, Shao-Fan; Li, Hai-Rong; Wang, Li-Zhen; Li, De-Zhu; Yang, Lin-Sheng; Li, Chong-Zheng

    2003-01-01

    AIM: To observe dynamic of different chemical elements in stomach tissue during fetal development. METHODS: To determine contents of the 21 chemical elements in each stomach samples from fetus aging four to ten months. The content values were compared to those from adult tissue samples, and the values for each month group were also analyzed for dynamic changes. RESULTS: Three representations were found regarding the relationship between contents of the elements and ages of the fetus, including the positive correlative (K), reversely correlative (Na, Ca, P, Al, Cu, Zn, Fe, Mn, Cr, Sr, Li, Cd, Ba, Se) and irrelevant groups (Mg, Co, Ni, V, Pb, Ti). CONCLUSION: The chemical elements’ contents in stomach tissues were found to change dynamically with the stomach weights. The age-dependent representations for different chemical elements during the prenatal development may be of some significance for assessing development of fetal stomach and some chemical elements. The data may be helpful for the nutritional balance of fetus and mothers during prenatal development and even the perinatal stages. PMID:12717857

  2. Reactive molecular dynamics simulation and chemical kinetic modeling of pyrolysis and combustion of n-dodecane

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Quan-De [College of Chemistry, Sichuan University, Chengdu (China); Wang, Jing-Bo; Li, Juan-Qin; Tan, Ning-Xin; Li, Xiang-Yuan [College of Chemical Engineering, Sichuan University, Chengdu (China)

    2011-02-15

    The initiation mechanisms and kinetics of pyrolysis and combustion of n-dodecane are investigated by using the reactive molecular dynamics (ReaxFF MD) simulation and chemical kinetic modeling. From ReaxFF MD simulations, we find the initiation mechanisms of pyrolysis of n-dodecane are mainly through two pathways, (1) the cleavage of C-C bond to form smaller hydrocarbon radicals, and (2) the dehydrogenation reaction to form an H radical and the corresponding n-C{sub 12}H{sub 25} radical. Another pathway is the H-abstraction reactions by small radicals including H, CH{sub 3}, and C{sub 2}H{sub 5}, which are the products after the initiation reaction of n-dodecane pyrolysis. ReaxFF MD simulations lead to reasonable Arrhenius parameters compared with experimental results based on first-order kinetic analysis of n-dodecane pyrolysis. The density/pressure effects on the pyrolysis of n-dodecane are also analyzed. By appropriate mapping of the length and time from macroscopic kinetic modeling to ReaxFF MD, a simple comparison of the conversion of n-dodecane from ReaxFF MD simulations and that from kinetic modeling is performed. In addition, the oxidation of n-dodecane is studied by ReaxFF MD simulations. We find that formaldehyde molecule is an important intermediate in the oxidation of n-dodecane, which has been confirmed by kinetic modeling, and ReaxFF leads to reasonable reaction pathways for the oxidation of n-dodecane. These results indicate that ReaxFF MD simulations can give an atomistic description of the initiation mechanism and product distributions of pyrolysis and combustion for hydrocarbon fuels, and can be further used to provide molecular based robust kinetic reaction mechanism for chemical kinetic modeling of hydrocarbon fuels. (author)

  3. Effect of a high strength chemical industry wastewater on microbial community dynamics and mesophilic methane generation.

    Science.gov (United States)

    Venkatakrishnan, Harish; Tan, Youming; Majid, Maszenan Bin Abdul; Pathak, Santosh; Sendjaja, Antonius Yudi; Li, Dongzhe; Liu, Jerry Jian Lin; Zhou, Yan; Ng, Wun Jern

    2014-04-01

    A high strength chemical industry wastewater was assessed for its impact on anaerobic microbial community dynamics and consequently mesophilic methane generation. Cumulative methane production was 251 mL/g total chemical oxygen demand removed at standard temperature and pressure at the end of 30 days experimental period with a highest recorded methane percentage of 80.6% of total biogas volume. Volatile fatty acids (VFAs) analysis revealed that acetic acid was the major intermediate VFAs produced with propionic acid accumulating over the experimental period. Quantitative analysis of microbial communities in the test and control groups with quantitative real time polymerase chain reaction highlighted that in the test group, Eubacteria (96.3%) was dominant in comparison with methanogens (3.7%). The latter were dominated by Methanomicrobiales and Methanobacteriales while Methanosarcinaceae in test groups increased over the experimental period, reaching a maximum on day 30. Denaturing gradient gel electrophoresis profile was performed, targeting the 16S rRNA gene of Eubacteria and Archaea, with the DNA samples extracted at 3 different time points from the test groups. A phylogenetic tree was constructed for the sequences using the neighborhood joining method. The analysis revealed that the presence of organisms resembling Syntrophomonadaceae could have contributed to increased production of acetic and propionic acid intermediates while decrease of organisms resembling Pelotomaculum sp. could have most likely contributed to accumulation of propionic acid. This study suggested that the degradation of organic components within the high strength industrial wastewater is closely linked with the activity of certain niche microbial communities within eubacteria and methanogens.

  4. Super-resolution chemical imaging with dynamic placement of plasmonic hotspots

    Science.gov (United States)

    Olson, Aeli P.; Ertsgaard, Christopher T.; McKoskey, Rachel M.; Rich, Isabel S.; Lindquist, Nathan C.

    2015-08-01

    We demonstrate dynamic placement of plasmonic "hotspots" for super-resolution chemical imaging via Surface Enhanced Raman Spectroscopy (SERS). A silver nanohole array surface was coated with biological samples and illuminated with a laser. Due to the large plasmonic field enhancements, blinking behavior of the SERS hotspots was observed and processed using a Stochastic Optical Reconstruction Microscopy (STORM) algorithm enabling localization to within 10 nm. However, illumination of the sample with a single static laser beam (i.e., a slightly defocused Gaussian beam) only produced SERS hotspots in fixed locations on the surface, leaving noticeable gaps in any final image. But, by using a spatial light modulator (SLM), the illumination profile of the beam could be altered, shifting any hotspots across the nanohole array surface in sub-wavelength steps. Therefore, by properly structuring an illuminating light field with the SLM, we show the possibility of positioning plasmonic hotspots over a metallic nanohole surface on-the-fly. Using this and our SERS-STORM imaging technique, we show potential for high-resolution chemical imaging without the noticeable gaps that were present with static laser illumination. Interestingly, even illuminating the surface with randomly shifting SLM phase profiles was sufficient to completely fill in a wide field of view for super-resolution SERS imaging of a single strand of 100-nm thick collagen protein fibrils. Images were then compared to those obtained with a scanning electron microscope (SEM). Additionally, we explored alternative methods of phase shifting other than holographic illumination through the SLM to create localization of hotspots necessary for SERS-STORM imaging.

  5. Chemical crosslinking and mass spectrometry studies of the structure and dynamics of membrane proteins and receptors.

    Energy Technology Data Exchange (ETDEWEB)

    Haskins, William E.; Leavell, Michael D.; Lane, Pamela; Jacobsen, Richard B.; Hong, Joohee; Ayson, Marites J.; Wood, Nichole L.; Schoeniger, Joseph S.; Kruppa, Gary Hermann; Sale, Kenneth L.; Young, Malin M.; Novak, Petr

    2005-03-01

    Membrane proteins make up a diverse and important subset of proteins for which structural information is limited. In this study, chemical cross-linking and mass spectrometry were used to explore the structure of the G-protein-coupled photoreceptor bovine rhodopsin in the dark-state conformation. All experiments were performed in rod outer segment membranes using amino acid 'handles' in the native protein sequence and thus minimizing perturbations to the native protein structure. Cysteine and lysine residues were covalently cross-linked using commercially available reagents with a range of linker arm lengths. Following chemical digestion of cross-linked protein, cross-linked peptides were identified by accurate mass measurement using liquid chromatography-fourier transform mass spectrometry and an automated data analysis pipeline. Assignments were confirmed and, if necessary, resolved, by tandem MS. The relative reactivity of lysine residues participating in cross-links was evaluated by labeling with NHS-esters. A distinct pattern of cross-link formation within the C-terminal domain, and between loop I and the C-terminal domain, emerged. Theoretical distances based on cross-linking were compared to inter-atomic distances determined from the energy-minimized X-ray crystal structure and Monte Carlo conformational search procedures. In general, the observed cross-links can be explained by re-positioning participating side-chains without significantly altering backbone structure. One exception, between C3 16 and K325, requires backbone motion to bring the reactive atoms into sufficient proximity for cross-linking. Evidence from other studies suggests that residues around K325 for a region of high backbone mobility. These findings show that cross-linking studies can provide insight into the structural dynamics of membrane proteins in their native environment.

  6. Isotopic and impurity element probes of mesoscale chemical dynamics at mineral fluid interfaces

    Science.gov (United States)

    DePaolo, D. J.

    2012-12-01

    Mesoscale interactions control important Earth processes including the growth of minerals from aqueous solutions and silicate liquids, the diffusion of ions in solids and silicate liquids, and the solid-state deformation and recrystallization that constitutes metamorphism. Most of these processes are typically understood from the classical side in terms of macroscopic physical and thermodynamic properties and classical kinetics, and from the molecular side in terms of single molecule or nearest-neighbor interactions. However, in many cases the controlling processes occur at intermediate scales of both length and time, and involve complex interactions among multiple chemical species. A major limitation has been in characterizing and modeling the dynamic processes that lead to the macroscopic properties and behavior. Advanced microscopy techniques allow phase changes, for example, to be monitored at high resolution, and this capability continues to improve. However, other important information about the phase changes, such as the molecular exchange fluxes between phases and the detailed mechanisms of reaction, are not revealed by microscopy. High-resolution isotopic characterization now allows the molecular exchange fluxes to be quantified, and models suggest that the incorporation of impurity elements is directly tied to these fluxes. One of the main advances is that precise isotopic measurements have recently been extended to include major stoichiometric cations such as Ca, Mg, Fe, and K, as well as key impurity elements such as U, Cd, Mo, and Sr. Isotopic analysis at the nano- to microscale would further clarify the detailed dynamics of mineral chemistry controls but are not yet possible except in a few instances. Impurity element concentrations are more easily measured at these small scales, and they are a key bridge between isotopic measurements and microscopy.Other limitations to advancing our knowledge of the chemical and isotopic effects associated with

  7. Dynamics, chemical properties and bioavailability of DOC in an early successional catchment

    Directory of Open Access Journals (Sweden)

    U. Risse-Buhl

    2013-07-01

    Full Text Available The dynamics of dissolved organic carbon (DOC have been intensively studied in mature ecosystems, but little is known about DOC dynamics and the significance of DOC as a substrate for microbial activity in early-successional catchments. We determined the concentration, chemical composition, source, radiocarbon age, and bioavailability of DOC along the hydrological flow path from soil solution to a downstream pond in a recently constructed catchment (Chicken Creek Catchment, Germany. Soil solution, upwelling ground water, stream water, subsurface water in an alluvial fan, and pond water all had high DOC concentrations (averages: 6.0–11.6 mg DOC L–1, despite small carbon stocks in both vegetation and soil of the catchment. Solid-state CPMAS 13C NMR of DOC in upwelling ground water revealed a higher proportion of aromatic compounds (32% and a lower proportion of carbohydrates (33% than in pond water (18% and 45%, respectively. The average 14C age of DOC in upwelling ground water was 2600 to 2900 yr, while organic matter of the Quaternary substrate of the catchment had a 14C age of 3000 to 16 000 yr. Both the 14C age data and 13C NMR spectra suggest that DOC partly derived from organic matter of the Quaternary substrate (about 40 to 90% of the C in the DOC, indicating that both recent and old C of the DOC can support microbial activity during early ecosystem succession. However, in a 70 day incubation experiment, only about 11% of the total DOC was found to be bioavailable. This proportion was irrespective of the water type. Origin of the microbial communities within the catchment (enriched from soil, stream sediment or pond water also had only a marginal effect on overall DOC utilization.

  8. Dynamics, chemical properties and bioavailability of DOC in an early successional catchment

    Directory of Open Access Journals (Sweden)

    U. Risse-Buhl

    2013-01-01

    Full Text Available The dynamics of dissolved organic carbon (DOC have been intensively studied in mature ecosystems, but little is known about DOC dynamics and the significance of DOC as a substrate for microbial activity in early-successional catchments. We determined the concentration, chemical composition, source, radiocarbon age, and bioavailability of DOC along the hydrological flow path from soil solution to a downstream pond in a recently constructed catchment (Chicken Creek Catchment, Germany. Soil solution, upwelling ground water, subsurface water in an alluvial fan, and pond water all had high DOC concentrations (averages of 6.0–11.6 mg DOC L−1, despite small carbon stocks in either vegetation or soil of the early-successional catchment. The mean 14C age of DOC in upwelling ground water was 2600 to 2800 yr. Solid-state CPMAS 13C NMR revealed a higher proportion of aromatic compounds (32% and a lower proportion of carbohydrates (33% in upwelling ground water than in pond water (18% and 45%, respectively. The 14C age and 13C NMR spectra suggest that DOC was partly mobilized from charred organic matter of the Quaternary substrate. In an experimental 70-days incubation experiment, 20% of the total DOC was found to be bioavailable, irrespective of the water type. Origin of microbial communities (enriched from soil, stream sediment or pond water had only marginal effects on overall DOC utilization. Overall, these data suggest that the old DOC can support microbial activity during early ecosystem succession to some extent, although the largest fraction is recalcitrant DOC that is exported from the catchment once it has been mobilized.

  9. Frictional melting dynamics in the upper conduit: A chemical answer to a complex physical question

    Science.gov (United States)

    Henton De Angelis, S.; Lavallee, Y.; Kendrick, J. E.; Hornby, A.; von Aulock, F. W.; Clesham, S.; Hirose, T.; Perugini, D.

    2013-12-01

    During volcanic eruptions the generation of frictional heat along the walls of the shallow conduit leads to melting of the rocks along the slip interface. Frictional melting has previously been described as a process out of thermodynamic equilibrium, but upon slip and mingling of the melt batches, homogeneity can be achieved, and may have an h important rheological control on the dynamics of slip. To test melt homogenization in the frictional melt zones of volcanic conduits we performed constant-rate slip experiments under controlled stress conditions using a high-velocity rotary shear apparatus. Volcanic dome samples from three different volcanoes (Volcán De Colima, Soufrière Hills Volcano and Santiaguito Volcano) were investigated. Each sample was subjected to a stress of 1 MPa and slip rate of 1 m/s. For each sample set 5 experiments were conducted: 1) experiment stopped at the onset of melting; 2) experiment stopped on the formation of a full melt layer; 3) experiment stopped after 5m of slip at steady state conditions; 4) experiment stopped after 10m of slip at steady state conditions; 5) experiment stopped after 15m of slip at steady state conditions. We analyzed the resulting proto-melt zones using micron sized X-ray spectroscopy in the high-brightness synchrotron beamline I18 (at Diamond Light Source UK). Particular focus was given to the concentration variance analysis of Rare Earth Elements as their mobilities can be used to precisely quantify the degree and timescale of homogenisation involved during frictional melting. This study refines our understanding of the chemical process of melting and mixing which carry important consequences for the rheological control on the physical dynamics of slip.

  10. Population dynamics, information transfer, and spatial organization in a chemical reaction network under spatial confinement and crowding conditions

    Science.gov (United States)

    Bellesia, Giovanni; Bales, Benjamin B.

    2016-10-01

    We investigate, via Brownian dynamics simulations, the reaction dynamics of a generic, nonlinear chemical network under spatial confinement and crowding conditions. In detail, the Willamowski-Rossler chemical reaction system has been "extended" and considered as a prototype reaction-diffusion system. Our results are potentially relevant to a number of open problems in biophysics and biochemistry, such as the synthesis of primitive cellular units (protocells) and the definition of their role in the chemical origin of life and the characterization of vesicle-mediated drug delivery processes. More generally, the computational approach presented in this work makes the case for the use of spatial stochastic simulation methods for the study of biochemical networks in vivo where the "well-mixed" approximation is invalid and both thermal and intrinsic fluctuations linked to the possible presence of molecular species in low number copies cannot be averaged out.

  11. Population dynamics, information transfer, and spatial organization in a chemical reaction network under spatial confinement and crowding conditions.

    Science.gov (United States)

    Bellesia, Giovanni; Bales, Benjamin B

    2016-10-01

    We investigate, via Brownian dynamics simulations, the reaction dynamics of a generic, nonlinear chemical network under spatial confinement and crowding conditions. In detail, the Willamowski-Rossler chemical reaction system has been "extended" and considered as a prototype reaction-diffusion system. Our results are potentially relevant to a number of open problems in biophysics and biochemistry, such as the synthesis of primitive cellular units (protocells) and the definition of their role in the chemical origin of life and the characterization of vesicle-mediated drug delivery processes. More generally, the computational approach presented in this work makes the case for the use of spatial stochastic simulation methods for the study of biochemical networks in vivo where the "well-mixed" approximation is invalid and both thermal and intrinsic fluctuations linked to the possible presence of molecular species in low number copies cannot be averaged out.

  12. Chemical and Microbial Dynamics during Composting of Herbal Pharmaceutical Industrial Waste

    Directory of Open Access Journals (Sweden)

    Farhan Zameer

    2010-01-01

    Full Text Available A study was performed to analyze the dynamics of chemical, biochemical and microbial parameters during composting of herbal pharmaceutical waste. All the parameters were analyzed at three different intervals of composting (1st, 15th and 60th days. Temperature of the compost pile was initially high (46.2 °C and on 60th day it dropped to 33.3 °C. The pH of the sample was initially acidic (2.39 and with the progress of decomposition gradually changed to neutrality (7.55. Electrical conductivity (EC value was high (3.8 mS during last day of composting compared to other stages. The activity of degradative enzymes namely amylase, invertase and urease were initially high (4.1, 4.79 mg of glucose/g/h and 0.19 mg of ammonia/g/h respectively while it decreased with composting. The beneficial microbial load was initially low and very high at the last stages of decomposition. The bioassay studies using compost extracts revealed that the 60th day old sample was not phytotoxic in nature.

  13. Solving chemical dynamic optimization problems with ranking-based differential evolution algorithms

    Institute of Scientific and Technical Information of China (English)

    Xu Chen; Wenli Du; Feng Qian

    2016-01-01

    Dynamic optimization problems (DOPs) described by differential equations are often encountered in chemical engineering. Deterministic techniques based on mathematic programming become invalid when the models are non-differentiable or explicit mathematical descriptions do not exist. Recently, evolutionary algorithms are gaining popularity for DOPs as they can be used as robust alternatives when the deterministic techniques are in-valid. In this article, a technology named ranking-based mutation operator (RMO) is presented to enhance the previous differential evolution (DE) algorithms to solve DOPs using control vector parameterization. In the RMO, better individuals have higher probabilities to produce offspring, which is helpful for the performance enhancement of DE algorithms. Three DE-RMO algorithms are designed by incorporating the RMO. The three DE-RMO algorithms and their three original DE algorithms are applied to solve four constrained DOPs from the literature. Our simulation results indicate that DE-RMO algorithms exhibit better performance than previous non-ranking DE algorithms and other four evolutionary algorithms.

  14. The imprint of satellite accretion on the chemical and dynamical properties of disc galaxies

    CERN Document Server

    Ruiz-Lara, T; Gibson, B K; Pérez, I; Florido, E; Minchev, I; Sánchez-Blázquez, P

    2015-01-01

    Aims: We study the effects of the cosmological assembly history on the chemical and dynamical properties of the discs of spiral galaxies as a function of radius. Methods: We make use of the simulated Milky-Way mass, fully-cosmological discs, from {\\tt RaDES} (Ramses Disc Environment Study). We analyse their assembly history by examining the proximity of satellites to the galactic disc, instead of their merger trees, to better gauge which satellites impact the disc. We present stellar age and metallicity profiles, Age-Metallicity Relation (AMR), Age-Velocity dispersion Relation (AVR), and Stellar Age Distribution (SAD) in several radial bins for the simulated galaxies. Results: Assembly histories can be divided into three different stages: i) a merger dominated phase, when a large number of mergers with mass ratios of $\\sim$1:1 take place (lasting $\\sim$3.2$\\pm$0.4 Gyr on average); ii) a quieter phase, when $\\sim$1:10 mergers take place (lasting $\\sim$4.4$\\pm$2.0 Gyr) - these two phases are able to kinematical...

  15. Chemical Dynamics Simulations of Intermolecular Energy Transfer: Azulene + N2 Collisions.

    Science.gov (United States)

    Kim, Hyunsik; Paul, Amit K; Pratihar, Subha; Hase, William L

    2016-07-14

    Chemical dynamics simulations were performed to investigate collisional energy transfer from highly vibrationally excited azulene (Az*) in a N2 bath. The intermolecular potential between Az and N2, used for the simulations, was determined from MP2/6-31+G* ab initio calculations. Az* is prepared with an 87.5 kcal/mol excitation energy by using quantum microcanonical sampling, including its 95.7 kcal/mol zero-point energy. The average energy of Az* versus time, obtained from the simulations, shows different rates of Az* deactivation depending on the N2 bath density. Using the N2 bath density and Lennard-Jones collision number, the average energy transfer per collision ⟨ΔEc⟩ was obtained for Az* as it is collisionally relaxed. By comparing ⟨ΔEc⟩ versus the bath density, the single collision limiting density was found for energy transfer. The resulting ⟨ΔEc⟩, for an 87.5 kcal/mol excitation energy, is 0.30 ± 0.01 and 0.32 ± 0.01 kcal/mol for harmonic and anharmonic Az potentials, respectively. For comparison, the experimental value is 0.57 ± 0.11 kcal/mol. During Az* relaxation there is no appreciable energy transfer to Az translation and rotation, and the energy transfer is to the N2 bath.

  16. Transcending race?

    DEFF Research Database (Denmark)

    Wilson, Fiona

    2007-01-01

    Using accounts of militant schoolteachers from a province in the central sierra of Peru, this article attempts to show how and why concepts of race and political commitment among teachers changed at three critical moments in Peruvian history: agrarian reform, mass unionisation, and Maoist insurge...

  17. Transcending Transmission

    DEFF Research Database (Denmark)

    Schoeneborn, Dennis; Trittin, Hannah

    2013-01-01

    of connectivity of CSR to other practices of organizational communication. Communication practices that concern CSR should not be generally dismissed as mere “greenwashing” – given that some forms of talk can be action. Consequently, there is a need to investigate which specific speech acts create accountability...

  18. Transcending functional boundaries: the cultural, strategic, and tactical domains of marketing.

    Science.gov (United States)

    Rapert, M I; Babakus, E; Olson, J

    1997-01-01

    While debate in the health care literature continues with respect to the role of marketing, many industries are adopting a broadened perspective which recognizes the comprehensive role which marketing may assume at a variety of levels within the organization: marketing as culture, marketing as strategy, and marketing as tactics. A national study of general service hospitals suggests that, in many hospitals, the marketing function is indeed transcending its functional boundaries through enculturation of a marketing orientation, involvement in the strategic process of the organization, and expansion of tactical marketing activities. Hospitals which adopt and support this broadened role of marketing are witnessing a positive effect on performance.

  19. The new frontier of religion and science religious experience, neuroscience, and the transcendent

    CERN Document Server

    Hick, J

    2006-01-01

    If you take for granted the widespread assumption of our culture that matter constitutes the totality of reality, this book will challenge that assumption. The pervasive materialist or physicalist presupposition of so much thinking is not scientifically established but is a basic article of naturalistic faith. Professor Hick argues that the widely held belief that consciousness is identical with or a by-product of the functioning of the brain is unsustainable. There is non-physical as well as physical reality. It is entirely possible that there is a divine realm transcending the material unive

  20. G.H. Franz’s Modjadji : archetypes of time and the transcendence of history

    Directory of Open Access Journals (Sweden)

    L.P. Boshego

    2009-07-01

    Full Text Available This article examines the Northern Sotho play, “Modjadji”, written by G.H. Franz. The text, about which there is little significant critical literature, presents in mythological terms the quest of the Lobedu rain queen, Modjadji, for secure governance and release from the exigencies of history, both for herself and her people. Through staged ritual, the play evokes archetypes of time to raise a mythic consciousness. This ontology employs a notion of circular time to transcend linearity and its inexorable teleology. Ultimately, the text attempts to extract viable elements of traditional epistemology in order to accommodate its addressees to modernity.

  1. Oscillations and multiscale dynamics in a closed chemical reaction system: second law of thermodynamics and temporal complexity.

    Science.gov (United States)

    Li, Yongfeng; Qian, Hong; Yi, Yingfei

    2008-10-21

    We investigate the oscillatory reaction dynamics in a closed isothermal chemical system: the reversible Lotka-Volterra model. The second law of thermodynamics dictates that the system ultimately reaches an equilibrium. Quasistationary oscillations are analyzed while the free energy of the system serves as a global Lyapunov function of the dissipative dynamics. A natural distinction between regions near and far from equilibrium in terms of the free energy can be established. The dynamics is analogous to a nonlinear mechanical system with time-dependent increasing damping. Near equilibrium, no oscillation is possible as dictated by Onsager's reciprocal symmetry relation. We observe that while the free energy decreases in the closed system's dynamics, it does not follow the steepest descending path.

  2. The imprint of satellite accretion on the chemical and dynamical properties of disc galaxies

    Science.gov (United States)

    Ruiz-Lara, T.; Few, C. G.; Gibson, B. K.; Pérez, I.; Florido, E.; Minchev, I.; Sánchez-Blázquez, P.

    2016-02-01

    Aims: We study the effects of the cosmological assembly history on the chemical and dynamical properties of the discs of spiral galaxies as a function of radius. Methods: We made use of the simulated Milky Way mass, fully-cosmological discs from Ramses Disc Environment Study (RaDES). We analysed their assembly history by examining the proximity of satellites to the galactic disc, instead of their merger trees, to better gauge which satellites impact the disc. We presented stellar age and metallicity profiles, age-metallicity relation (AMR), age-velocity dispersion relation (AVR), and stellar age distribution (SAD) in several radial bins for the simulated galaxies. Results: Assembly histories can be divided into three different stages: i) a merger dominated phase, when a large number of mergers with mass ratios of ~1:1 take place (lasting ~3.2 ± 0.4 Gyr on average); ii) a quieter phase, when ~1:10 mergers take place (lasting ~4.4 ± 2.0 Gyr); and iii) a secular phase where the few mergers that take place have mass ratios below 1:100, which do not affect the disc properties (lasting ~5.5 ± 2.0 Gyr). The first two phases are able to kinematically heat the disc and produce a disc that is chemically mixed over its entire radial extension. Phase 2 ends with a final merger event (at time tjump) marking the onset of important radial differences in the AMR, AVR, and SAD. Conclusions: Inverted AMR trends in the outer parts of discs, for stars younger than tjump, are found as the combined effect of radial motions and star formation in satellites temporarily located in these outer parts. U-shaped stellar age profiles change to an old plateau (~10 Gyr) in the outer discs for the entire RaDES sample. This shape is a consequence of inside-out growth of the disc, radial motions of disc stars (inwards and outwards), and the accretion of old stars from satellites. We see comparable age profiles even when ignoring the influence of stellar migration due to the presence of early in

  3. Chemical communication and dynamics of droplet emulsions in networks of Belousov-Zhabotinsky micro-oscillators produced by microfluidics.

    Science.gov (United States)

    Torbensen, Kristian; Rossi, Federico; Ristori, Sandra; Abou-Hassan, Ali

    2017-03-29

    Chemical communication leading to synchronization and collective behaviour of dynamic elements, such as cell colonies, is a widespread phenomenon with biological, physical and chemical importance. Such synchronization between elements proceeds via chemical communication by emmision, interdiffusion and reception of specific messenger molecules. On a lab scale, these phenomena can be modeled by encapsulating an oscillating chemical reaction, which serves as a signal (information) sender/receiver element, inside microcompartments such as droplet emulsions, liposomes and polymersomes. Droplets can thus be regarded as single units, able to generate chemical messengers that diffuse in the environment and hence can interact with other compartments. The Belousov-Zhabotinsky (BZ) reaction is a well-known chemical oscillator largely used as a model for complex nonlinear phenomena, including chemical, physical and biological examples. When the BZ-reaction is encapsulated inside microcompartments, its chemical intermediates can serve as messengers by diffusing among different microcompartments, to trigger specific reactions leading to a collective behavior between the elements. The geometry and constitution of the diffusion pathways play an important role in governing the collective behaviour of the system. In this context, microfluidics is not only a versatile tool for mastering the encapsulation process of the BZ-reaction in monodisperse microcompartments, but also for creating geometries and networks with well defined boundaries. The individual compartments can be engineered with selected properties using different surfactants in the case of simple emulsions, or with specific membrane properties in the case of liposomes. Furthermore, it enables the arrangement of these microcompartments in various geometric configurations, where the diffusive coupling pathways between individual compartments are both spatially and chemically well-defined. In this tutorial paper, we review a

  4. Universal imaging: Dissociative ionization of polyatomic molecules, chemical dynamics beamline 9.0.2

    Energy Technology Data Exchange (ETDEWEB)

    Ahmed, M.; Chen, D.; Suits, A.G. [Ernest Orlando Lawrence Berkeley National Lab., CA (United States)

    1997-04-01

    A third endstation was recently added to the Chemical Dynamics beamline, designed to exploit the high flux broadband undulator light for a range of studies of reactive scattering, photochemistry and photoionization processes using time-of-flight mass spectroscopy coupled with position-sensitive detection. Two molecular beam sources are fixed at right angles, with the undulator light, or laser beams, intersecting the molecular beams at 45{degrees}. To date, beamline experiments have included a study of dissociative photoionization of a variety of molecules including N{sub 2}O and SF{sub 6}. In this mode, a single molecular beam source is used, with the tunable undulator light inducing, in SF{sub 6} for example, the process SF{sub 6} {r_arrow} SF{sub 6}{sup +} + e{sup {minus}} {r_arrow} SF{sub 5}{sup +} + F + e{sup {minus}}. The SF{sub 5}{sup +} ions are accelerated up the flight tube, mass selected and detected as a function of position on a phosphor screen viewed by a CCD camera. The position directly reveals the recoil speed (or translational energy release) and angular distribution for the dissociative ionization process. Furthermore, this measurement is obtained for all recoil speeds and angles simultaneously. Such detailed angular information has not previously been obtained for dissociative ionization processes; typically ion time-of-flight profiles are deconvoluted to yield rough insight into the angular distributions. The recorded image is actually a 2-dimensional projection of the nascent 3-dimensional velocity distribution, but established tomographic techniques enable the authors to reconstruct the 3-D distribution.

  5. Attribution of ozone changes to dynamical and chemical processes in CCMs and CTMs

    Directory of Open Access Journals (Sweden)

    H. Garny

    2011-01-01

    Full Text Available Chemistry-climate models (CCMs are commonly used to simulate the past and future development of Earth's ozone layer. The fully coupled chemistry schemes calculate the chemical production and destruction of ozone interactively and ozone is transported by the simulated atmospheric flow. Due to the complexity of the processes acting on ozone it is not straightforward to disentangle the influence of individual processes on the temporal development of ozone concentrations. A method is introduced here that quantifies the influence of chemistry and transport on ozone concentration changes and that is easily implemented in CCMs and chemistry-transport models (CTMs. In this method, ozone tendencies (i.e. the time rate of change of ozone are partitioned into a contribution from ozone production and destruction (chemistry and a contribution from transport of ozone (dynamics. The influence of transport on ozone in a specific region is further divided into export of ozone out of that region and import of ozone from elsewhere into that region. For this purpose, a diagnostic is used that disaggregates the ozone mixing ratio field into 9 separate fields according to in which of 9 predefined regions of the atmosphere the ozone originated. With this diagnostic the ozone mass fluxes between these regions are obtained. Furthermore, this method is used here to attribute long-term changes in ozone to chemistry and transport. The relative change in ozone from one period to another that is due to changes in production or destruction rates, or due to changes in import or export of ozone, are quantified. As such, the diagnostics introduced here can be used to attribute changes in ozone on monthly, interannual and long-term time-scales to the responsible mechanisms. Results from a CCM simulation are shown here as examples, with the main focus of the paper being on introducing the method.

  6. Nonlinear Hamiltonian mechanics applied to molecular dynamics theory and computational methods for understanding molecular spectroscopy and chemical reactions

    CERN Document Server

    Farantos, Stavros C

    2014-01-01

    This brief presents numerical methods for describing and calculating invariant phase space structures, as well as solving the classical and quantum equations of motion for polyatomic molecules. Examples covered include simple model systems to realistic cases of molecules spectroscopically studied. Vibrationally excited and reacting molecules are nonlinear dynamical systems, and thus, nonlinear mechanics is the proper theory to elucidate molecular dynamics by investigating invariant structures in phase space. Intramolecular energy transfer, and the breaking and forming of a chemical bond have now found a rigorous explanation by studying phase space structures.

  7. 1H NMR study of the solvent THF concerning their structural and dynamical properties in chemically Li-intercalated SWNT

    KAUST Repository

    Schmid, Marc R.

    2011-09-01

    Structural and dynamical properties of the THF solvent in single-walled carbon nanotubes intercalated with lithium are investigated by NMR. 1H NMR experiments reveal the existence of two types of inequivalent THF solvent molecules with different chemical environments and dynamical behavior. At low temperatures THF molecules perpendicularly arranged in between adjacent SWNT presumably exhibit a restricted rotation around their dipolar axis. At higher temperatures THF molecules are isotropically rotating and diffusing along the interstitial channels of the SWNT bundles. © 2011 Elsevier B.V. All rights reserved.

  8. Nanoscale Chemical Imaging of a Dynamic Molecular Phase Boundary with Ultrahigh Vacuum Tip-Enhanced Raman Spectroscopy.

    Science.gov (United States)

    Jiang, Nan; Chiang, Naihao; Madison, Lindsey R; Pozzi, Eric A; Wasielewski, Michael R; Seideman, Tamar; Ratner, Mark A; Hersam, Mark C; Schatz, George C; Van Duyne, Richard P

    2016-06-08

    Nanoscale chemical imaging of a dynamic molecular phase boundary has broad implications for a range of problems in catalysis, surface science, and molecular electronics. While scanning probe microscopy (SPM) is commonly used to study molecular phase boundaries, its information content can be severely compromised by surface diffusion, irregular packing, or three-dimensional adsorbate geometry. Here, we demonstrate the simultaneous chemical and structural analysis of N-N'-bis(2,6-diisopropylphenyl)-1,7-(4'-t-butylphenoxy)perylene-3,4:9,10-bis(dicarboximide) (PPDI) molecules by UHV tip-enhanced Raman spectroscopy. Both condensed and diffusing domains of PPDI coexist on Ag(100) at room temperature. Through comparison with time-dependent density functional theory simulations, we unravel the orientation of PPDI molecules at the dynamic molecular domain boundary with unprecedented ∼4 nm spatial resolution.

  9. 个体记忆的道德超越%Moral Transcendence of Individual Memory

    Institute of Scientific and Technical Information of China (English)

    刘大先

    2015-01-01

    从华兹华斯以来,记忆与个人主义的关联一直越系越紧,从文学蔓延及历史。记忆只有从个体道德超越,跃升到真正伦理的层面,才有可能恢复它真正的活力与意义。记忆的平权意味着不仅让曾被压抑者获得申言的机会,也给它的对手以辩论的机会。同时在集体性的社会关怀之下,知识分子应该超越自身一己的悲欢情感,才有可能塑造出一个良性的记忆语境。%Since Wordsworth time, memory and individualism are closely related to each other, stretching out from literature to history. Only when it transcends from individual morality to the real ethical level can memory regain its vitality and significance. The equal rights of memory provides opportunities both for the repressed to speak out their ideas and for their rivals to argue about it. With the collective social care, intellectuals should transcend their own joys and sorrows so as to create a benignant memory.

  10. Union with the transcendent God in Philo and John’s Gospel

    Directory of Open Access Journals (Sweden)

    Pieter G.R. de Villiers

    2014-02-01

    Full Text Available This article analyses the experience of divine presence within an intimate divine-human relationship, as conceptualised in Philo’s writings, and compares this experience with mystical passages in John’s Gospel. The article explains their understanding of God and how the union with a transcendent God is mediated. The article investigates this union in terms of an underlying mystical pattern that existed in the 1st century CE. The pattern explains similarities of Philo’s works with John’s Gospel that indicates the former’s mystical nature. Special attention is given to Philo’s accounts because his own mystical experiences and views are relatively unknown in New Testament scholarship, whilst John’s Gospel is compared to show how this pattern existed within a Jewish-Christian setting. After an introduction to the relevance of mysticism in contemporary research on Philo and John, the article, without trying to establish any genetic link between Philo and John, evaluates the understanding of mystical union in the light of Philo’s own mystical experience and pronouncements. Then follows a discussion of Philo’s understanding of the divine longing for union with humanity despite the divine transcendence, with attention to the direct and indirect manner in which this union is mediated. Finally, similar motifs in John’s Gospel are investigated.

  11. Induction of strain-transcending immunity against Plasmodium chabaudi adami malaria with a multiepitope DNA vaccine.

    Science.gov (United States)

    Scorza, T; Grubb, K; Smooker, P; Rainczuk, A; Proll, D; Spithill, T W

    2005-05-01

    A major goal of current malaria vaccine programs is to develop multivalent vaccines that will protect humans against the many heterologous malaria strains that circulate in endemic areas. We describe a multiepitope DNA vaccine, derived from a genomic Plasmodium chabaudi adami DS DNA expression library of 30,000 plasmids, which induces strain-transcending immunity in mice against challenge with P. c. adami DK. Segregation of this library and DNA sequence analysis identified vaccine subpools encoding open reading frames (ORFs)/peptides of >9 amino acids [aa] (the V9+ pool, 303 plasmids) and >50 aa (V50+ pool, 56 plasmids), respectively. The V9+ and V50+ plasmid vaccine subpools significantly cross-protected mice against heterologous P. c. adami DK challenge, and protection correlated with the induction of both specific gamma interferon production by splenic cells and opsonizing antibodies. Bioinformatic analysis showed that 22 of the V50+ ORFs were polypeptides conserved among three or more Plasmodium spp., 13 of which are predicted hypothetical proteins. Twenty-nine of these ORFs are orthologues of predicted Plasmodium falciparum sequences known to be expressed in the blood stage, suggesting that this vaccine pool encodes multiple blood-stage antigens. The results have implications for malaria vaccine design by providing proof-of-principle that significant strain-transcending immunity can be induced using multiepitope blood-stage DNA vaccines and suggest that both cellular responses and opsonizing antibodies are necessary for optimal protection against P. c. adami.

  12. Self-Transcendence Values, Relationships, and Participatory Practice in Early Childhood Education

    Directory of Open Access Journals (Sweden)

    Clodie Tal

    2014-01-01

    Full Text Available This study seeks to reveal the circumstances that encourage versus those that block children’s participation in the context of daily teacher-children encounters in preschools in Israel. Six cases were selected for analysis—three in which children’s participation was enabled and three in which children’s participation was blocked by teachers or student-teachers. Participants in the study were five student-teachers doing fieldwork as part of their professional preparation as well as two teachers. Analysis yielded the following conclusions: meaningful participation takes place in the context of a personal, caring relationship with an educator. For challenging situations that require decisions about enabling or denying children’s participation, self-transcendence values need to be activated by student-teachers or teachers. Activation of these values is the outcome of personal mental struggle, which is strengthened by having clear, articulated goals to include children in guided and nonguided social encounters. This study suggests that a teacher’s espousal of self-transcendence values is among the attributes that have an impact on teachers’ representations of relationships, their interactions with children, and the children’s participation in daily, preschool social encounters, whose quality may in turn affect the relationships with children. Documentation and critical reflection need to be incorporated into educational practice so that decision-making in challenging situations will be the product of thorough deliberation.

  13. Use of the social competence interview and the anger transcendence challenge in individuals with alcohol use disorder.

    Science.gov (United States)

    Maisto, Stephen A; Ewart, Craig K; Connors, Gerard J; Funderburk, Jennifer S; Krenek, Marketa

    2009-06-01

    Interpersonal stress is a significant determinant of relapse following treatment for Alcohol Use Disorders (AUDs), but there remains little specific information about the mechanisms underlying the relationship between interpersonal stress and AUD relapse. Application of Social Action Theory provides one new approach to advancing knowledge about the interpersonal stress-relapse relationship. Especially relevant are the Social Action Theory construct of social-emotional competence, with its accompanying measurement procedures of the Social Competence Interview and the Anger Transcendence Challenge. This study evaluated the use of the Social Competence Interview and Anger Transcendence Challenge in a sample of 63 men and women in AUD intensive outpatient treatment. The results support the use of the Social Competence Interview and the Anger Transcendence Challenge with an adult AUD clinical sample, so that these measures may help to advance knowledge about the relationship between interpersonal stress and alcohol relapse.

  14. A Coupled Dynamical Model of Redox Flow Battery Based on Chemical Reaction, Fluid Flow, and Electrical Circuit

    OpenAIRE

    Li, Minghua; Hikihara, Takashi

    2008-01-01

    The redox (Reduction-Oxidation) flow battery is one of the most promising rechargeable batteries due to its ability to average loads and output of power sources. The transient characteristics are well known as the remarkable feature of the battery. Then it can also compensate for a sudden voltage drop. The dynamics are governed by the chemical reactions, fluid flow, and electrical circuit of its structure. This causes the difficulty of the analysis at transient state. This paper discusses the...

  15. Prediction of the Chapman–Jouguet chemical equilibrium state in a detonation wave from first principles based reactive molecular dynamics

    OpenAIRE

    Guo, Dezhou; Zybin, Sergey V.; An, Qi; Goddard, William A.; Huang, Fenglei

    2016-01-01

    The combustion or detonation of reacting materials at high temperature and pressure can be characterized by the Chapman–Jouguet (CJ) state that describes the chemical equilibrium of the products at the end of the reaction zone of the detonation wave for sustained detonation. This provides the critical properties and product kinetics for input to macroscale continuum simulations of energetic materials. We propose the ReaxFF Reactive Dynamics to CJ point protocol (Rx2CJ) for predicting the CJ s...

  16. Transcending intractable conflict in health care: an exploratory study of communication and conflict management among anesthesia providers.

    Science.gov (United States)

    Jameson, Jessica Katz

    2003-01-01

    This paper explores the contrast between the longstanding, intractable conflict between two anesthesia providers and the cooperation of many individual nurse anesthetists and anesthesiologists working side-by-side to provide safe, effective anesthesia. Analysis of interview transcripts reveals that communication among anesthesia nurses and anesthesiologists may enact or transcend the conflict. This article proposes recommendations for improving communication between anesthesiologists and certified registered nurse anesthetists in particular and de-escalating intractable conflict in general. It also contributes to communication theory in intractable conflict by examining how individual, interpersonal conflict management interactions lead to either transcendence or enactment of the larger group conflict.

  17. Painlevé transcendent describes quantum correlation function of the XXZ antiferromagnet away from the free-fermion point

    CERN Document Server

    Essler, F H L; Its, A R; Korepin, V E; Essler, Fabian H L; Frahm, Holger; Its, Alexander R; Korepin, Vladimir E

    1996-01-01

    We consider quantum correlation functions of the antiferromagnetic spin-\\frac{1}{2} Heisenberg XXZ spin chain in a magnetic field. We show that for a magnetic field close to the critical field h_c (for the critical magnetic field the ground state is ferromagnetic) certain correlation functions can be expressed in terms of the solution of the Painlev\\'e V transcendent. This establishes a relation between solutions of Painlev\\'e differential equations and quantum correlation functions in models of {\\sl interacting} fermions. Painlev\\'e transcendents were known to describe correlation functions in models with free fermionic spectra.

  18. The Influence of Seasonal Changes and Headwaters on Physico-chemical Dynamics of Temengor Reservoir, Malaysia%The Influence of Seasonal Changes and Headwaters on Physico-chemical Dynamics of Temengor Reservoir,Malaysia

    Institute of Scientific and Technical Information of China (English)

    Zarul Hazrin Hashim; Asmah Patiroi; Mashhor Mansor; Shahml Anuar Md. Sah; Donald C. Jackson

    2011-01-01

    A study on physico-chemical dynamics of Temengor Reservoir was conducted to determine whether headwaters and seasonal changes play a major role in regulating physico-chemical dynamics of Temengor Reservoir.Temengor Reservoir receives water from its surrounding water catchments and headwaters.Then,the water flows into a series of hydroelectric dams,namely the Bersia,Kenering and Chenderoh dams.Generally,water quality in Temengot Reservoir can be classified as Class I.Physico-chemical trends showed that water quality in euphoric zone of Temengor Reservoir is stable and consistent.Two-way ANOVA analyses showed that seasonal variations only affected water temperature,Secchi disc's depth and nitrate-nitrogen.Based on Tukey' s post-hoc test,all three headwaters in this study exert no influence to the reservoir's water quality.These insignificant differences were probably due to water temperature and the size of the headwaters and the reservoir itself.In situ parameters profiling showed that the epilirrmion zone in Temengor Reservoir is from the surface to 6 m depth,the metalirrmion zone is from 6 m to 12 m depth and the hypolimnion zone is from 12 m depth onwards to the bottom of the reservoir.Thus,continuous water profiling monitoring that covers high and low water levels need to be conducted to determine characteristics of the physico-chemical dynamics in the water column and also to analyse changes in reservoir layers.Through these studies,discontinuity trends in the Perak River could be determined and suggestions to the respective agencies could be made to conserve and to sustain downstream biodiversity.

  19. The multiscale simulation of metal organic chemical vapor deposition growth dynamics of GaInP thin film

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    As a Group III–V compound, GaInP is a high-efficiency luminous material. Metal organic chemical vapor deposition (MOCVD) technology is a very efficient way to uniformly grow multi-chip, multilayer and large-area thin film. By combining the computational fluid dynamics (CFD) and the kinetic Monte Carlo (KMC) methods with virtual reality (VR) technology, this paper presents a multiscale simulation of fluid dynamics, thermodynamics, and molecular dynamics to study the growth process of GaInP thin film in a vertical MOCVD reactor. The results of visualization truly and intuitively not only display the distributional properties of the gas’ thermal and flow fields in a MOCVD reactor but also display the process of GaInP thin film growth in a MOCVD reactor. The simulation thus provides us with a fundamental guideline for optimizing GaInP MOCVD growth.

  20. Ultrafast infrared studies of chemical reaction dynamics in room-temperature liquids

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Haw [Univ. of California, Berkeley, CA (United States)

    1999-11-01

    Femtosecond infrared spectroscopy provides sufficient spectral and temporal resolution to support a detailed investigation of the early events of a photochemical reaction. Previously unreported transient species that arise as intermediates during the course of a reaction may have lifetimes that are too short for conventional characterization. For these species, quantum-mechanical (density functional theoretical and ab initio) electronic structure calculations provide invaluable insight into chemical properties including molecular structure and energetic. With the combination of experimental and theoretical results, it is possible to assemble a comprehensive picture of the reaction dynamics of a system that is intricately influenced by the surrounding solvent molecules. The mechanisms of several important organometallic reactions, such as alkane C– H bond activation by η3-Tp*Rh(CO), silane Si–H bond activation by η5-CpMn(CO)2 and η5-CpRe(CO)2, as well as chlorinated methane C–Cl bond cleavage by the Re(CO)5 radical are elucidated. The results demonstrate the importance of molecular morphology change (C–H and Si–H act ivat ion), solvent rearrangement (Si–H activation), intersystem crossing (Si–H activation), and solvent caging (C–Cl cleavage) in understanding the reactivity of the organometallic species, The nature of the apparent free-energy barrier for C–H, Si–H, and C–Cl bond activation reaction is found to be- cleavage of an alkane C–H bond, rearrangement of a silane molecule HSiR3 (R = alkyl group) from a nonreactive alkyl site to the reactive Si–H bond, and Cl atom transfer from a chlorinated methane molecule to Re(CO)5, respectively. These results support previous d initio calculations for C–H and Si–H bond activation reaction profiles which suggest that cleavage of an alkane C–H bond by a transition metal center, unlike that of a silane

  1. Microbial dynamics during and after in situ chemical oxidation of chlorinated solvents

    NARCIS (Netherlands)

    Sutton, N.B.; Atashgahi, S.; Wal, van der J.; Wijn, G.; Grotenhuis, J.T.C.; Smidt, H.; Rijnaarts, H.

    2015-01-01

    In situ chemical oxidation (ISCO) followed by a bioremediation step is increasingly being considered as an effective biphasic technology. Information on the impact of chemical oxidants on organohalide respiring bacteria (OHRB), however, is largely lacking. Therefore, we used quantitative PCR (qPCR)

  2. Coupled molecular dynamics-Monte Carlo model to study the role of chemical processes during laser ablation of polymeric materials.

    Science.gov (United States)

    Prasad, Manish; Conforti, Patrick F; Garrison, Barbara J

    2007-08-28

    The coarse grained chemical reaction model is enhanced to build a molecular dynamics (MD) simulation framework with an embedded Monte Carlo (MC) based reaction scheme. The MC scheme utilizes predetermined reaction chemistry, energetics, and rate kinetics of materials to incorporate chemical reactions occurring in a substrate into the MD simulation. The kinetics information is utilized to set the probabilities for the types of reactions to perform based on radical survival times and reaction rates. Implementing a reaction involves changing the reactants species types which alters their interaction potentials and thus produces the required energy change. We discuss the application of this method to study the initiation of ultraviolet laser ablation in poly(methyl methacrylate). The use of this scheme enables the modeling of all possible photoexcitation pathways in the polymer. It also permits a direct study of the role of thermal, mechanical, and chemical processes that can set off ablation. We demonstrate that the role of laser induced heating, thermomechanical stresses, pressure wave formation and relaxation, and thermochemical decomposition of the polymer substrate can be investigated directly by suitably choosing the potential energy and chemical reaction energy landscape. The results highlight the usefulness of such a modeling approach by showing that various processes in polymer ablation are intricately linked leading to the transformation of the substrate and its ejection. The method, in principle, can be utilized to study systems where chemical reactions are expected to play a dominant role or interact strongly with other physical processes.

  3. Dynamics of chemical vapor sensing with MoS2 using 1T/2H phase contacts/channel

    Science.gov (United States)

    Friedman, Adam L.; Perkins, F. Keith; Hanbicki, Aubrey T.; Culbertson, James C.; Campbell, Paul M.

    2016-06-01

    Ultra-thin transition metal dichalcogenides (TMDs) films show remarkable potential for use in chemical vapor sensing devices. Electronic devices fabricated from TMD films are inexpensive, inherently flexible, low-power, amenable to industrial-scale processing because of emergent growth techniques, and have shown high sensitivity and selectivity to electron donor analyte molecules important for explosives and nerve gas detection. However, for devices reported to date, the conductance response to chemical vapors is dominated by Schottky contacts, to the detriment of the sensitivity, selectivity, recovery, and obscuring their intrinsic behavior. Here, we use contact engineering to transition the contacts in a MoS2 FET-based chemical vapor sensor to the 1T conducting phase, while leaving the channel in the 2H semiconducting state, and thus providing Ohmic contacts to the film. We demonstrate that the resultant sensors have much improved electrical characteristics, are more selective, and recover fully after chemical vapor exposure--all major enhancements to previously MoS2 sensor devices. We identify labile nitrogen-containing electron donors as the primary species that generate a response in MoS2, and we study the dynamics of the sensing reactions, identifying two possible qualitative models for the chemical sensing reaction.

  4. Arterial Stiffness and Pharmacological Interventions – The TRanscend Arterial stiffNess Substudy (TRANS study

    Directory of Open Access Journals (Sweden)

    Jirar Topouchian

    2007-09-01

    Full Text Available Jirar Topouchian1, Ramzi El Feghali1, Bruno Pannier1, Shuyu Wang2, Feng Zhao3, Karel Smetana4, Koon Teo3, Roland Asmar11The CardioVascular Institute, Paris, France; 2Beijing Clinical Trial and Research Center, Beijing, China; 3Population Health Research Institute, Hamilton, Canada; 4Vojenska nemocnice Plzen, Pizen, Czech RepublicAbstract: The degree of arterial stiffness is correlated with the risk of cardiovascular diseases and it is a powerful predictor for morbidity and mortality. Studies have shown that arterial stiffness reduction is associated with an improvement in survival. Reduction of arterial stiffness by pharmacological drugs varies according to the drugs and doses used and duration of treatment. This effect on the arteries differs among the various classes of drugs and among individual drugs in the same class. Quantification of the stiffness and other properties of the arterial wall can be used to monitor the responses to therapy in individuals with hypertension and other cardiovascular diseases. These measures can then be used as surrogate markers for the risk of clinical events. Inhibition of the renin-angiotensin system (RAS is associated with an important decrease in cardiovascular risk. Findings from clinical trials support the hypothesis that the protective effects of RAS inhibition are partly independent from blood pressure reduction and related to several mechanisms including vascular protective effects. The aim of the TRanscend Arterial stiffNess Substudy (TRANS is to assess the effect of an angiotensin II receptor blocker (ARB, telmisartan, on the arterial stiffness in a subgroup of patients from the Telmisartan Randomized Assessment Study in aCE iNtolerant subjects with cardiovascular Disease (TRANSCEND trial. The TRANSCEND trial is an international, multicenter, randomized double blind placebo controlled trial of telmisartan that enrolled patients at high risk for cardiovascular events. Some clinical baseline data of the

  5. Complex Langevin dynamics for dynamical QCD at nonzero chemical potential: a comparison with multi-parameter reweighting

    CERN Document Server

    Fodor, Z; Sexty, D; Török, C

    2015-01-01

    We study lattice QCD at non-vanishing chemical potential using the complex Langevin equation. We compare the results with multi-parameter reweighting both from $\\mu=0$ and phase quenched ensembles. We find a good agreement for lattice spacings below $\\approx$0.15 fm. On coarser lattices the complex Langevin approach breaks down. Four flavors of staggered fermions are used on $N_t=4, 6$ and 8 lattices. For one ensemble we also use two flavors to investigate the effects of rooting.

  6. Quantitative chemical tagging, stellar ages and the chemo-dynamical evolution of the Galactic disc

    CERN Document Server

    Mitschang, A W; Zucker, D B; Anguiano, B; Bensby, T; Feltzing, S

    2013-01-01

    The early science results from the new generation of high-resolution stellar spectroscopic surveys, such as GALAH and the Gaia-ESO survey, will represent major milestones in the quest to chemically tag the Galaxy. Yet this technique to reconstruct dispersed coeval stellar groups has remained largely untested until recently. We build on previous work that developed an empirical chemical tagging probability function, which describes the likelihood that two field stars are conatal, that is, they were formed in the same cluster environment. In this work we perform the first ever blind chemical tagging experiment, i.e., tagging stars with no known or otherwise discernable associations, on a sample of 714 disc field stars with a number of high quality high resolution homogeneous metal abundance measurements. We present evidence that chemical tagging of field stars does identify coeval groups of stars, yet these groups may not represent distinct formation sites, e.g. as in dissolved open clusters, as previously thou...

  7. Discrete matrix models for partial sums of conformal blocks associated to Painlev\\'e transcendents

    CERN Document Server

    Balogh, F

    2014-01-01

    A recently formulated conjecture of Gamayun, Iorgov and Lisovyy gives an asymptotic expansion of the Jimbo--Miwa--Ueno isomonodromic $\\tau$-function for certain Painlev\\'e transcendents. The coefficients in this expansion are given in terms of conformal blocks of a two-dimensional conformal field theory, which can be written as infinite sums over pairs of partitions. In this note a discrete matrix model is proposed on a lattice whose partition function can be used to obtain a multiple integral representation for the length restricted partial sums of the Painlev\\'e conformal blocks. This leads to expressions of the partial sums involving H\\"ankel determinants associated to the discrete measure of the matrix model, or equivalently, Wronskians of the corresponding moment generating function which is shown to be of the generalized hypergeometric type.

  8. Transcendência e Antropologia do Cristianismo: linguagem, mudança e individualismo

    Directory of Open Access Journals (Sweden)

    Joel Robbins

    2011-06-01

    Full Text Available Nas últimas décadas, temos presenciado o surgimento de uma Antropologia do Cristianismo. Destacam-se, nesse campo emergente, as seguintes questões-chave: 1 o papel do Cristianismo em esforços de promoção de mudança social; 2 o caráter distintivo das interpretações Cristãs sobre a linguagem; 3 a tendência do Cristianismo a fomentar o individualismo. Este artigo oferece um relato sintético desses precessos considerando como as diversas interpretações cristãs da tensão entre transcendência e mundano conformam as maneiras pelas quais diversas igrejas lidam com essas questões.

  9. Balancing Tradition and Transcendence in the Implementation of Emergency-Department Electronic Whiteboads

    DEFF Research Database (Denmark)

    Rasmussen, Rasmus; Fleron, Benedicte; Hertzum, Morten

    2010-01-01

    We report from a case study of the implementation of an electronic whiteboard system at two emergency departments at Danish hospitals. The purpose of the whiteboards is to support the clinicians in maintaining an overview of the patients at the departments. The electronic whiteboard system...... was designed in collaboration with clinicians from the departments. Compared to existing dry-erase whiteboards, the electronic whiteboards present more information and allow some automated updating. Based on observations supported by interviews we describe how tradition and transcendence were balanced...... in the implementation of the whiteboards at the two emergency departments. The electronic whiteboards were initially configured to resemble the dry-erase whiteboards and then gradually reconfigured and extended through an improvisational process, along with changes in the clinicians’ work practices....

  10. Identity, transcendence and the true self: Insights from psychology and contemplative spirituality

    Directory of Open Access Journals (Sweden)

    Carter Haynes

    2016-05-01

    Full Text Available This article investigates the intersection of psychology and spirituality as seen through the works of Thomas Merton, Carl Jung, Fritz Kunkel and Viktor Frankl. The themes of spirituality contextualised in human identity, psychological and spiritual transcendence, and the true self versus false self metaphor are traced through the works of all four thinkers. Epistemological flexibility and holistic thinking and being are suggested as methods for transforming interdisciplinary practitioners, such as pastoral counsellors, spiritual directors and spiritually oriented psychotherapists, in order that they can offer care in a less bifurcated and more integrated way. Practical applications, including a vignette and specific recommendations for broadening and deepening personal and professional integrative practice, are offered.

  11. READING IN THE DARK: THE TRANSCENDENCE OF POLITICAL REALITY THROUGH ART

    Directory of Open Access Journals (Sweden)

    Aída Díaz Bild

    2002-12-01

    Full Text Available In the last three decades scholars coming from the most different fields have defended the positive, regenerating and creative qualities of the comic mode. Laughter is an agent of transcendence, a vehicle for coping with the hardships of life, a valuable talisman which allows us to survive in a world hedged with the threat of every horror and every ignominy. Reading zn the Dark, by Seamus Deane, is a very clear example of a novel in which humour helps to mitigate the harshness of the difficult and painful situations that are described, so that at the end of the book the spirit of life triumphs over death and sadness. By exploiting the narrator's naivety Deane plays down false sentimentalism and melodrama and prevents the reader from falling into despair.

  12. Four Paths to Spirit at Work: Journeys of Personal Meaning, Fulfillment, Well-Being, and Transcendence through Work

    Science.gov (United States)

    Kinjerski, Val; Skrypnek, Berna J.

    2008-01-01

    Spirit at work involves profound feelings of well-being, a belief that one's work makes a contribution, a sense of connection to others and common purpose, an awareness of a connection to something larger than self, and a sense of perfection and transcendence. This exploratory qualitative study revealed 4 paths leading to spirit at work: the…

  13. Raising Awareness to Transcend Disciplines: Developing Teachers' Critical Awareness across Disciplines to Increase Indigenous Learner Engagement

    Science.gov (United States)

    Riley, Tasha

    2014-01-01

    The issue of low graduation rates among Indigenous learners transcends borders. Some argue that racism and discrimination in schools and in wider society impede the success of Indigenous learners. Although teachers may not intend to make discriminatory decisions based on a learner's ascribed characteristics, research has demonstrated that…

  14. Determination of the Orientation and Dynamics of Ergosterol in Model Membranes Using Uniform 13C Labeling and Dynamically Averaged 13C Chemical Shift Anisotropies as Experimental Restraints

    Science.gov (United States)

    Soubias, O.; Jolibois, F.; Massou, S.; Milon, A.; Réat, V.

    2005-01-01

    A new strategy was established to determine the average orientation and dynamics of ergosterol in dimyristoylphosphatidylcholine model membranes. It is based on the analysis of chemical shift anisotropies (CSAs) averaged by the molecular dynamics. Static 13C CSA tensors were computed by quantum chemistry, using the gauge-including atomic-orbital approach within Hartree-Fock theory. Uniformly 13C-labeled ergosterol was purified from Pichia pastoris cells grown on labeled methanol. After reconstitution into dimyristoylphosphatidylcholine lipids, the complete 1H and 13C assignment of ergosterol's resonances was performed using a combination of magic-angle spinning two-dimensional experiments. Dynamically averaged CSAs were determined by standard side-band intensity analysis for isolated 13C resonances (C3 and ethylenic carbons) and by off-magic-angle spinning experiments for other carbons. A set of 18 constraints was thus obtained, from which the sterol's molecular order parameter and average orientation could be precisely defined. The validity of using computed CSAs in this strategy was verified on cholesterol model systems. This new method allowed us to quantify ergosterol's dynamics at three molar ratios: 16 mol % (Ld phase), 30 mol % (Lo phase), and 23 mol % (mixed phases). Contrary to cholesterol, ergosterol's molecular diffusion axis makes an important angle (14°) with the inertial axis of the rigid four-ring system. PMID:15923221

  15. Role of tip chemical reactivity on atom manipulation process in dynamic force microscopy.

    Science.gov (United States)

    Sugimoto, Yoshiaki; Yurtsever, Ayhan; Abe, Masayuki; Morita, Seizo; Ondráček, Martin; Pou, Pablo; Pérez, Ruben; Jelínek, Pavel

    2013-08-27

    The effect of tip chemical reactivity on the lateral manipulation of intrinsic Si adatoms toward a vacancy site on a Si(111)-(7 × 7) surface has been investigated by noncontact atomic force microscopy at room temperature. Here we measure the atom-hopping probabilities associated with different manipulation processes as a function of the tip-surface distance by means of constant height scans with chemically different types of tips. The interactions between different tips and Si atoms are evaluated by force spectroscopic measurements. Our results demonstrate that the ability to manipulate Si adatoms depends extremely on the chemical nature of the tip apex and is correlated with the maximal attractive force measured over Si adatoms. We rationalize the observed dependence of the atom manipulation process on tip-apex chemical reactivity by means of density functional theory calculations. The results of these calculations suggest that the ability to reduce the energy barrier associated with the Si adatom movement depends profoundly on tip chemical reactivity and that the level of energy barrier reduction is higher with tips that exhibit high chemical reactivity with Si adatoms. The results of this study provide a better way to control the efficiency of the atomic manipulation process for chemisorption systems.

  16. Conceptual Pathways to Ethnic Transcendence in Diverse Churches: Theoretical Reflections on the Achievement of Successfully Integrated Congregations

    Directory of Open Access Journals (Sweden)

    Gerardo Marti

    2015-09-01

    Full Text Available The concept of ethnic transcendence—defined as the process of co-formulating a shared religious identity among diverse members that supersedes their racial and ethnic differences through congregational involvement—captures a critical aspect of successfully integrating different racial and ethnic groups into a single, commonly shared, multi-ethnic congregation. Drawing on classic theoretical resources from Max Weber and Emile Durkheim, this paper expands on previous scholarship by conceptually articulating two different paths for the achievement of ethnic transcendence in multiracial congregations. In the first path, ethnic transcendence supports and encourages congregational diversification by inspiring members and mobilizing them to contribute their efforts to accomplish a common religious mission. In the second path, the achievement of ethnic transcendence involves the sublimation of congregational members’ religious selves to an overarching moral collective. Both paths involve privileging religious identities in favor of a particularistic ethnic or racial identity. Moreover, through both paths, the development of congregationally specific religious identities results in joining with co-members of different ethno-racial ancestries as a type of spiritually-derived kinship. Due to the fact that ethnic transcendence is an interactive process, congregational diversity is a bi-directional phenomenon representing the extent to which members allow for the integration of separate ethnicities/races into a common congregation through idealized and richly-symbolic notions of connection and belonging to a congregation. Overall, this paper suggests a heuristic framework that productively expands the concept of ethnic transcendence, allows an approach for observing cross-ethnic/inter-racial organizational processes, and ultimately contributes toward understanding how congregations (whether church, temple, or mosque pursue alternative identity

  17. Stochastic dynamics and non-equilibrium thermodynamics of a bistable chemical system: the Schlögl model revisited.

    Science.gov (United States)

    Vellela, Melissa; Qian, Hong

    2009-10-06

    Schlögl's model is the canonical example of a chemical reaction system that exhibits bistability. Because the biological examples of bistability and switching behaviour are increasingly numerous, this paper presents an integrated deterministic, stochastic and thermodynamic analysis of the model. After a brief review of the deterministic and stochastic modelling frameworks, the concepts of chemical and mathematical detailed balances are discussed and non-equilibrium conditions are shown to be necessary for bistability. Thermodynamic quantities such as the flux, chemical potential and entropy production rate are defined and compared across the two models. In the bistable region, the stochastic model exhibits an exchange of the global stability between the two stable states under changes in the pump parameters and volume size. The stochastic entropy production rate shows a sharp transition that mirrors this exchange. A new hybrid model that includes continuous diffusion and discrete jumps is suggested to deal with the multiscale dynamics of the bistable system. Accurate approximations of the exponentially small eigenvalue associated with the time scale of this switching and the full time-dependent solution are calculated using Matlab. A breakdown of previously known asymptotic approximations on small volume scales is observed through comparison with these and Monte Carlo results. Finally, in the appendix section is an illustration of how the diffusion approximation of the chemical master equation can fail to represent correctly the mesoscopically interesting steady-state behaviour of the system.

  18. Phase Diagram of Dynamical Twisted Mass Wilson Fermions at Finite Isospin Chemical Potential

    CERN Document Server

    Janssen, Oliver; Splittorff, K; Verbaarschot, Jacobus J M; Zafeiropoulos, Savvas

    2015-01-01

    We consider the phase diagram of twisted mass Wilson fermions of two-flavor QCD in the parameter space of the quark mass, the isospin chemical potential, the twist angle and the lattice spacing. This work extends earlier studies in the continuum and those at zero chemical potential. We evaluate the phase diagram as well as the spectrum of the (pseudo-)Goldstone bosons using the chiral Lagrangian for twisted mass Wilson fermions at non-zero isospin chemical potential. The phases are obtained from a mean field analysis. At zero twist angle we find that already an infinitesimal isospin chemical potential destroys the Aoki phase. The reason is that in this phase we have massless Goldstone bosons with a non-zero isospin charge. At finite twist angle only two different phases are present, one phase which is continuously connected to the Bose condensed phase at non-zero chemical potential and another phase which is continuously connected to the normal phase. For either zero or maximal twist the phase diagram is more...

  19. Chemical Dynamic Thermodynamic Resolution and S/R Interconversion of Unprotected Unnatural Tailor-made α-Amino Acids.

    Science.gov (United States)

    Wang, Shuni; Zhou, Shengbin; Wang, Jiang; Nian, Yong; Kawashima, Aki; Moriwaki, Hiroki; Aceña, José L; Soloshonok, Vadim A; Liu, Hong

    2015-10-16

    Described here is an advanced, general method for purely chemical dynamic thermodynamic resolution and S/R interconversion of unprotected tailor-made α-amino acids (α-AAs) through intermediate formation of the corresponding nickel(II)-chelated Schiff bases. The method features virtually complete stereochemical outcome, broad substrate generality (35 examples), and operationally convenient conditions allowing for large-scale preparation of the target α-AAs in enantiomerically pure form. Furthermore, the new type of nonracemizable axially chiral ligands can be quantitatively recycled and reused, rendering the whole process economically and synthetically attractive.

  20. High-power supersonic chemical lasers: gas-dynamic problems of operation of mobile systems with PRS

    Science.gov (United States)

    Boreysho, A. S.; Malkov, V. M.; Savin, A. V.

    2008-10-01

    Supersonic chemical lasers, such as HF /DF and COIL, have always been in the focus of special interest as the most powerful sources of continuous wave generation. Presently, autonomous mobile laser complexes (both air- and landbased) are being developed on the basis of SCL [1-3]. It is commonly accepted that SCL appeared, conditionally speaking, at the crossroads of a number of sciences: of physics - quantum electronics and physical kinetics; chemistry - combustion theory and chemical kinetics; classic optics - theory of resonators, aero-optics, and gas dynamics (there is a supersonic flow in the SCL channel). Due to this fact, all tasks and problems which could be resolved in the course of SCL development have complex character and could be considered as the next stage of complexity in comparison with the well known similar tasks which had been considered earlier. This is why they should be resolved anew with consideration of the specific aspects of the SCL processes. This is true for the gas-dynamic problems: new parameter areas, non-traditional channel geometry, consideration of new phenomena, etc.Supersonic chemical lasers, such as HF /DF and COIL, have always been in the focus of special interest as the most powerful sources of continuous wave generation. Presently, autonomous mobile laser complexes (both air- and landbased) are being developed on the basis of SCL [1-3]. It is commonly accepted that SCL appeared, conditionally speaking, at the crossroads of a number of sciences: of physics - quantum electronics and physical kinetics; chemistry - combustion theory and chemical kinetics; classic optics - theory of resonators, aero-optics, and gas dynamics (there is a supersonic flow in the SCL channel). Due to this fact, all tasks and problems which could be resolved in the course of SCL development have complex character and could be considered as the next stage of complexity in comparison with the well known similar tasks which had been considered earlier

  1. Probing the Gas-Phase Dynamics of Graphene Chemical Vapour Deposition using in-situ UV Absorption Spectroscopy

    DEFF Research Database (Denmark)

    Shivayogimath, Abhay; Mackenzie, David; Luo, Birong

    2017-01-01

    of multilayer nucleation when backstreaming is suppressed. These results point to an important and previously undescribed mechanism for multilayer nucleation, wherein higher-order gas-phase carbon species play an integral role. Our work highlights the importance of gas-phase dynamics in understanding......The processes governing multilayer nucleation in the chemical vapour deposition (CVD) of graphene are important for obtaining high-quality monolayer sheets, but remain poorly understood. Here we show that higher-order carbon species in the gas-phase play a major role in multilayer nucleation...

  2. Modelling static and dynamic behaviour of proton exchange membrane fuel cells on the basis of electro-chemical description

    Science.gov (United States)

    Ceraolo, M.; Miulli, C.; Pozio, A.

    A simplified dynamical model of a fuel cell of the proton exchange membrane (PEM) type, based on physical-chemical knowledge of the phenomena occurring inside the cell has been developed by the authors. The model has been implemented in the MATLAB/SIMULINK environment. Lab tests have been carried out at ENEA's laboratories; and a good agreement has been found between tests and simulations, both in static and dynamic conditions. In a previous study [M. Ceraolo, R. Giglioli, C. Miulli, A. Pozio, in: Proceedings of the 18th International Electric Fuel Cell and Hybrid Vehicle Symposium (EVS18), Berlin, 20-24 October 2001, p. 306] the basic ideas of the model, as well as its experimental validation have been published. In the present paper, the full implementation of the model is reported in detail. Moreover, a procedure for evaluating all the needed numerical parameters is presented.

  3. NATO Advanced Research Workshop on The Theory of Chemical Reaction Dynamics

    CERN Document Server

    1986-01-01

    The calculation of cross sections and rate constants for chemical reactions in the gas phase has long been a major problem in theoretical chemistry. The need for reliable and applicable theories in this field is evident when one considers the significant recent advances that have been made in developing experimental techniques, such as lasers and molecular beams, to probe the microscopic details of chemical reactions. For example, it is now becoming possible to measure cross sections for chemical reactions state selected in the vibrational­ rotational states of both reactants and products. Furthermore, in areas such as atmospheric, combustion and interstellar chemistry, there is an urgent need for reliable reaction rate constant data over a range of temperatures, and this information is often difficult to obtain in experiments. The classical trajectory method can be applied routinely to simple reactions, but this approach neglects important quantum mechanical effects such as tunnelling and resonances. For al...

  4. Molecular beam studies of unimolecular and bimolecular chemical reaction dynamics using VUV synchrotron radiation as a product probe

    Energy Technology Data Exchange (ETDEWEB)

    Blank, David Andrew [Univ. of California, Berkeley, CA (United States)

    1997-08-01

    This dissertation describes the use of a new molecular beam apparatus designed to use tunable VUV synchrotron radiation for photoionization of the products from scattering experiments. The apparatus was built at the recently constructed Advanced Light Source at Lawrence Berkeley National Laboratory, a third generation 1-2 GeV synchrotron radiation source. The new apparatus is applied to investigations of the dynamics of unimolecular reactions, photodissociation experiments, and bimolecular reactions, crossed molecular beam experiments. The first chapter describes the new apparatus and the VUV radiation used for photoionization. This is followed by a number of examples of the many advantages provided by using VUV photoionization in comparison with the traditional technique of electron bombardment ionization. At the end of the chapter there is a discussion of the data analysis employed in these scattering experiments. The remaining four chapters are complete investigations of the dynamics of four chemical systems using the new apparatus and provide numerous additional examples of the advantages provided by VUV photoionizaiton of the products. Chapters 2-4 are photofragment translational spectroscopy studies of the photodissociation dynamics of dimethyl sulfoxide, acrylonitrile, and vinyl chloride following absorption at 193 mn. All of these systems have multiple dissociation channels and provide good examples of the ability of the new apparatus to unravel the complex UV photodissociation dynamics that can arise in small polyatomic molecules.

  5. In-Situ Chemical Dynamics and Phase Mapping Under Steep Thermal Gradients Using Time-Resolved and Spatially Resolved X-Ray Diffraction

    Energy Technology Data Exchange (ETDEWEB)

    Wong, J.; Larson, E.M.; Holt, J.B.; Ressler, T.; Elmer, J.W.

    1999-09-17

    Time-resolved and spatially-resolved diffraction techniques have been developed recently to perform materials dynamics study in-situ extending into the time and spatial domain in high temperature processes. The applications of these methods to investigate the chemical dynamics of solid combustion reactions and to map phases and their transformation in fusion welds are exemplified in this paper.

  6. Electron dynamics upon ionization: Control of the timescale through chemical substitution and effect of nuclear motion

    Energy Technology Data Exchange (ETDEWEB)

    Vacher, Morgane; Bearpark, Michael J.; Robb, Michael A. [Department of Chemistry, Imperial College London, London SW7 2AZ (United Kingdom); Mendive-Tapia, David [Laboratoire CEISAM - UMR CNR 6230, Université de Nantes, 2 Rue de la Houssinière, BP 92208, 44322 Nantes Cedex 3 (France)

    2015-03-07

    Photoionization can generate a non-stationary electronic state, which leads to coupled electron-nuclear dynamics in molecules. In this article, we choose benzene cation as a prototype because vertical ionization of the neutral species leads to a Jahn-Teller degeneracy between ground and first excited states of the cation. Starting with equal populations of ground and first excited states, there is no electron dynamics in this case. However, if we add methyl substituents that break symmetry but do not radically alter the electronic structure, we see charge migration: oscillations in the spin density that we can correlate with particular localized electronic structures, with a period depending on the gap between the states initially populated. We have also investigated the effect of nuclear motion on electron dynamics using a complete active space self-consistent field (CASSCF) implementation of the Ehrenfest method, most previous theoretical studies of electron dynamics having been carried out with fixed nuclei. In toluene cation for instance, simulations where the nuclei are allowed to move show significant differences in the electron dynamics after 3 fs, compared to simulations with fixed nuclei.

  7. Non-steady state mass action dynamics without rate constants: dynamics of coupled reactions using chemical potentials

    Science.gov (United States)

    Cannon, William R.; Baker, Scott E.

    2017-10-01

    Comprehensive and predictive simulation of coupled reaction networks has long been a goal of biology and other fields. Currently, metabolic network models that utilize enzyme mass action kinetics have predictive power but are limited in scope and application by the fact that the determination of enzyme rate constants is laborious and low throughput. We present a statistical thermodynamic formulation of the law of mass action for coupled reactions at both steady states and non-stationary states. The formulation uses chemical potentials instead of rate constants. When used to model deterministic systems, the method corresponds to a rescaling of the time dependent reactions in such a way that steady states can be reached on the same time scale but with significantly fewer computational steps. The relationships between reaction affinities, free energy changes and generalized detailed balance are central to the discussion. The significance for applications in systems biology are discussed as is the concept and assumption of maximum entropy production rate as a biological principle that links thermodynamics to natural selection.

  8. Developing a multimedia model of chemical dynamics in an urban area.

    Science.gov (United States)

    Diamond, M L; Priemer, D A; Law, N L

    2001-09-01

    A multimedia model has been developed to account for the movement of semi-volatile organic compounds (SOCs) in an urban environment. The model, based on a Level III fugacity model of D. Mackay (Multimedia Environmental Models: The Fugacity Approach, Lewis Publishers, Boca Raton, FL, 1991), consists of six compartments: air, surface water, sediment, soil, vegetation, and an organic film that coats impervious surfaces. The latter is a newly identified compartment into which gas-phase SOCs partition and particle-phase SOCs are believed to be efficiently captured (M.L. Diamond, S.E. Gingrich, K. Fertuck, B.E. McCarry, G.A. Stern, B. Billeck, B. Grift, D. Brooker, T.D. Yager, Environ. Sci. Technol., 34 (2000a), 2900-2908). The model, parameterized for downtown Toronto, Ontario, Canada, and run with an illustrative emission rate for selected polycyclic aromatic hydrocarbons and homologues of polychlorinated dibenzodioxins, indicates that the film achieves the highest concentrations among media but that soils are the greatest sink for all but the least hydrophobic chemicals. The film "reflects" the more volatile chemicals into air, facilitates removal to surface waters by wash-off, and provides a surface on which photolytic degradation can occur. As such, the film is a transient sink that increases chemical mobility in urban areas by increasing air concentrations and the cycling of these compounds between air and urban surfaces and increasing water concentrations. Vegetation also accumulates SOCs, a portion of which is transferred to soil that reduces chemical mobility.

  9. Material Cycles and Chemicals: Dynamic Material Flow Analysis of Contaminants in Paper Recycling

    DEFF Research Database (Denmark)

    Pivnenko, Kostyantyn; Laner, David; Astrup, Thomas Fruergaard

    2016-01-01

    This study provides a systematic approach for assessment of contaminants in materials for recycling. Paper recycling is used as an illustrative example. Three selected chemicals, bisphenol A (BPA), diethylhexyl phthalate (DEHP) and mineral oil hydrocarbons (MOHs), are evaluated within the paper...

  10. Do High School Chemistry Examinations Inhibit Deeper Level Understanding of Dynamic Reversible Chemical Reactions?

    Science.gov (United States)

    Wheeldon, R.; Atkinson, R.; Dawes, A.; Levinson, R.

    2012-01-01

    Background and purpose: Chemistry examinations can favour the deployment of algorithmic procedures like Le Chatelier's Principle (LCP) rather than reasoning using chemical principles. This study investigated the explanatory resources which high school students use to answer equilibrium problems and whether the marks given for examination answers…

  11. The VENUS/NWChem Software Package. Tight Coupling Between Chemical Dynamics Simulations and Electronic Structure Theory

    Energy Technology Data Exchange (ETDEWEB)

    Lourderaj, Upakarasamy; Sun, Rui; De Jong, Wibe A.; Windus, Theresa L.; Hase, William L.

    2014-03-01

    The interface for VENUS and NWChem, and the resulting software package for direct dynamics simulations are described. The coupling of the two codes is considered to be a tight coupling. The two codes are compiled and linked together and act as one executable with data being passed between the two codes through routine calls. The advantages of this type of coupling are discussed. The interface has been designed to have as little interference as possible with the core codes of both VENUS and NWChem. VENUS is the code that propagates the direct dynamics trajectories and, therefore, is the program that drives the overall execution of VENUS/NWChem. VENUS has remained an essentially sequential code, which uses the highly parallel structure of NWChem. Subroutines of the interface which accomplish the data transmission and communication between the two computer programs are described. Recent examples of the use of VENUS/NWChem for direct dynamics simulations are summarized.

  12. Chemical reactivity of the compressed noble gas atoms and their reactivity dynamics during collisions with protons

    Indian Academy of Sciences (India)

    P K Chattaraj; B Maiti; U Sarkar

    2003-06-01

    Attempts are made to gain insights into the effect of confinement of noble gas atoms on their various reactivity indices. Systems become harder, less polarizable and difficult to excite as the compression increases. Ionization also causes similar effects. A quantum fluid density functional technique is adopted in order to study the dynamics of reactivity parameters during a collision between protons and He atoms in different electronic states for various projectile velocities and impact parameters. Dynamical variants of the principles of maximum hardness, minimum polarizability and maximum entropy are found to be operative.

  13. The modelling of dynamic chemical state of paper machine unit operations; Dynaamisen kemiallisen tilan mallintaminen paperikoneen yksikkoeoperaatioissa - MPKT 04

    Energy Technology Data Exchange (ETDEWEB)

    Ylen, J.P.; Jutila, P. [Helsinki Univ. of Technology, Otaniemi (Finland)

    1998-12-31

    The chemical state of paper mass is considered to be a key factor to the smooth operation of the paper machine. There are simulators that have been developed either for dynamic energy and mass balances or for static chemical phenomena, but the combination of these is not a straight forward task. Control Engineering Laboratory of Helsinki University of Technology has studied the paper machine wet end phenomena with the emphasis on pH-modelling. VTT (Technical Research Centre of Finland) Process Physics has used thermodynamical modelling successfully in e.g. Bleaching processes. In this research the different approaches are combined in order to get reliable dynamical models and modelling procedures for various unit operations. A flexible pilot process will be constructed and different materials will be processed starting from simple inorganic substances (e.g. Calcium carbonate and distilled water) working towards more complex masses (thick pulp with process waters and various reagents). The pilot process is well instrumented with ion selective electrodes, total calcium analysator and all basic measurements. (orig.)

  14. Acceleration of the KINETICS Integrated Dynamical/Chemical Computational Model Using MPI

    Science.gov (United States)

    Grossman, Max; Willacy, Karen; Allen, Mark

    2011-01-01

    Understanding the evolution of a planet's atmosphere not only provides a better theoretical understanding of planetary physics and the formation of planets, but also grants useful insight into Earth's own atmosphere. One of the tools used at JPL for the modeling of planetary atmospheres and protostellar disks is KINETICS. KINETICS can simulate years of complex dynamics and chemistry.

  15. Acceleration of the KINETICS Integrated Dynamical/Chemical Computational Model Using MPI

    Science.gov (United States)

    Grossman, Max; Willacy, Karen; Allen, Mark

    2011-01-01

    Understanding the evolution of a planet's atmosphere not only provides a better theoretical understanding of planetary physics and the formation of planets, but also grants useful insight into Earth's own atmosphere. One of the tools used at JPL for the modeling of planetary atmospheres and protostellar disks is KINETICS. KINETICS can simulate years of complex dynamics and chemistry.

  16. Isotope effects in photodissociation: Chemical reaction dynamics and implications for atmospheres

    DEFF Research Database (Denmark)

    Jørgensen, Solvejg; Grage, Mette Marie-Louise; Nyman, Gunnar

    2008-01-01

    and implicitly involve the short time approximation. in the time-dependent methods the time-dependent Schrodinger equation is solved exactly and the method considers the effect of dynamics away from the Franck-Condon region. We illustrate the presented methods using small molecules (HCl, N2O, OCS and HCHO...

  17. Dynamics of the chemical composition and productivity of composts for the cultivation of Agaricus bisporus strains

    Directory of Open Access Journals (Sweden)

    Meire Cristina Nogueira de Andrade

    2013-12-01

    Full Text Available Two compost formulations based on oat straw (Avena sativa and brachiaria (Brachiaria sp. were tested for the cultivation of three Agaricus bisporus strains (ABI-07/06, ABI-05/03, and PB-1. The experimental design was a 2 x 3 factorial scheme (composts x strains with 6 treatments and 8 repetitions (boxes containing 12 kg of compost. The chemical characterization of the compost (humidity, organic matter, carbon, nitrogen, pH, raw protein, ethereal extract, fibers, ash, cellulose, hemicellulose, and lignin before and after the cultivation of A. bisporus and the production (basidiomata mass, productivity, and biological efficiency were evaluated. Data were submitted to variance analysis, and averages were compared by means of the Tukey's test. According to the results obtained, the chemical and production characteristics showed that the best performances for the cultivation of A. bisporus were presented by the compost based on oat and the strain ABI-07/06.

  18. Dynamics of the chemical composition and productivity of composts for the cultivation of Agaricus bisporus strains.

    Science.gov (United States)

    de Andrade, Meire Cristina Nogueira; de Jesus, João Paulo Furlan; Vieira, Fabrício Rocha; Viana, Sthefany Rodrigues Fernandes; Spoto, Marta Helena Fillet; de Almeida Minhoni, Marli Teixeira

    2013-12-01

    Two compost formulations based on oat straw (Avena sativa) and brachiaria (Brachiaria sp.) were tested for the cultivation of three Agaricus bisporus strains (ABI-07/06, ABI-05/03, and PB-1). The experimental design was a 2 × 3 factorial scheme (composts × strains) with 6 treatments and 8 repetitions (boxes containing 12 kg of compost). The chemical characterization of the compost (humidity, organic matter, carbon, nitrogen, pH, raw protein, ethereal extract, fibers, ash, cellulose, hemicellulose, and lignin) before and after the cultivation of A. bisporus and the production (basidiomata mass, productivity, and biological efficiency) were evaluated. Data were submitted to variance analysis, and averages were compared by means of the Tukey's test. According to the results obtained, the chemical and production characteristics showed that the best performances for the cultivation of A. bisporus were presented by the compost based on oat and the strain ABI-07/06.

  19. Molecular Mechanisms by Which Marine Phytoplankton Respond to Their Dynamic Chemical Environment

    Science.gov (United States)

    Palenik, Brian

    2015-01-01

    Marine scientists have long been interested in the interactions of marine phytoplankton with their chemical environments. Nutrient availability clearly controls carbon fixation on a global scale, but the interactions between phytoplankton and nutrients are complex and include both short-term responses (seconds to minutes) and longer-term evolutionary adaptations. This review outlines how genomics and functional genomics approaches are providing a better understanding of these complex interactions, especially for cyanobacteria and diatoms, for which the genome sequences of multiple model organisms are available. Transporters and related genes are emerging as the most likely candidates for biomarkers in stress-specific studies, but other genes are also possible candidates. One surprise has been the important role of horizontal gene transfer in mediating chemical-biological interactions.

  20. The spectroscopy and chemical dynamics of microparticles explored using an ultrasonic trap.

    Science.gov (United States)

    Mason, N J; Drage, E A; Webb, S M; Dawes, A; McPheat, R; Hayes, G

    2008-01-01

    Microsized particles play an important role in many diverse areas of science and technology, for example, surface reactions of micron-sized particles play a key role in astrochemistry, plasma reactors and atmospheric chemistry. To date much of our knowledge of such surface chemistry is derived from 'traditional' surface science-based research. However, the large surface area and morphology of surface material commonly used in such surface science techniques may not necessarily mimic that on the surface of micron/nano scale particles. Hence, a new generation of experiments in which the spectroscopy (e.g., albedo) and chemical reactivity of micron-sized particles can be studied directly must be developed. One, as yet underexploited, non-invasive technique is the use of ultrasonic levitation. In this article, we describe the operation of an 'ultrasonic trap' to store and study the physical and chemical properties of microparticles.

  1. Physically and chemically stable ionic liquid-infused textured surfaces showing excellent dynamic omniphobicity

    Directory of Open Access Journals (Sweden)

    Daniel F. Miranda

    2014-05-01

    Full Text Available A fluorinated and hydrophobic ionic liquid (IL, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl imide, effectively served as an advantageous lubricating liquid for the preparation of physically and chemically stable omniphobic surfaces based on slippery liquid-infused porous surfaces. Here, we used particulate microstructures as supports, prepared by the chemical vapor deposition of 1,3,5,7-tetramethylcyclotetrasiloxane and subsequent surface modification with (3-aminopropyltriethoxysilane. Confirmed by SEM and contact angle measurements, the resulting IL-infused microtextured surfaces are smooth and not only water but also various low surface tension liquids can easily slide off at low substrate tilt angles of <5°, even after exposure to high temperature, vacuum, and UV irradiation.

  2. Assessing the chemical contamination dynamics in a mixed land use stream system

    DEFF Research Database (Denmark)

    Sonne, Anne Thobo; McKnight, Ursula S.; Rønde, Vinni

    2017-01-01

    stressors in these systems and applied the approach to a 16-km groundwater-fed stream corridor (Grindsted, Denmark). Three methods were combined: (i) in-stream contaminant mass discharge for source quantification, (ii) Toxic Units and (iii) environmental standards. An evaluation of the chemical quality......Traditionally, the monitoring of streams for chemical and ecological status has been limited to surface water concentrations, where the dominant focus has been on general water quality and the risk for eutrophication. Mixed land use stream systems, comprising urban areas and agricultural production...... the stream water quality was substantially impaired by both geogenic and diffuse anthropogenic sources of metals along the entire corridor, while the streambed was less impacted. Quantification of the contaminant mass discharge originating from a former pharmaceutical factory revealed that several 100 kgs...

  3. Physically and chemically stable ionic liquid-infused textured surfaces showing excellent dynamic omniphobicity

    Energy Technology Data Exchange (ETDEWEB)

    Miranda, Daniel F.; Urata, Chihiro; Masheder, Benjamin; Dunderdale, Gary J.; Hozumi, Atsushi, E-mail: a.hozumi@aist.go.jp [National Institute of Advanced Industrial Science and Technology (AIST), 2266-98, Anagahora, Shimo-Shidami, Moriyama-ku, Nagoya, Aichi 463-8560 (Japan); Yagihashi, Makoto [Nagoya Municipal Industrial Research Institute, Rokuban, Atsuta-ku, Nagoya 456-0058 (Japan)

    2014-05-01

    A fluorinated and hydrophobic ionic liquid (IL), 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide, effectively served as an advantageous lubricating liquid for the preparation of physically and chemically stable omniphobic surfaces based on slippery liquid-infused porous surfaces. Here, we used particulate microstructures as supports, prepared by the chemical vapor deposition of 1,3,5,7-tetramethylcyclotetrasiloxane and subsequent surface modification with (3-aminopropyl)triethoxysilane. Confirmed by SEM and contact angle measurements, the resulting IL-infused microtextured surfaces are smooth and not only water but also various low surface tension liquids can easily slide off at low substrate tilt angles of <5°, even after exposure to high temperature, vacuum, and UV irradiation.

  4. A Graph Theoretical and Topological Approach to Chemical Structure, Reactivity, and Dynamics

    Science.gov (United States)

    1988-10-01

    chirality polynomial of the regular icosahedron, a problem previously assumed to be intractable. 2 7 Professor King has also expanded, extended, and...algebra to determine polynomials for the description of chirality observations. 6 0 This review presents a critical analysis of the limitations of...Surfaces: Such maps are generalizations of the convex polyhedra so common in chemical applications. During the last twenty years, Tutte and others have

  5. Polynomial-time quantum algorithm for the simulation of chemical dynamics.

    Science.gov (United States)

    Kassal, Ivan; Jordan, Stephen P; Love, Peter J; Mohseni, Masoud; Aspuru-Guzik, Alán

    2008-12-02

    The computational cost of exact methods for quantum simulation using classical computers grows exponentially with system size. As a consequence, these techniques can be applied only to small systems. By contrast, we demonstrate that quantum computers could exactly simulate chemical reactions in polynomial time. Our algorithm uses the split-operator approach and explicitly simulates all electron-nuclear and interelectronic interactions in quadratic time. Surprisingly, this treatment is not only more accurate than the Born-Oppenheimer approximation but faster and more efficient as well, for all reactions with more than about four atoms. This is the case even though the entire electronic wave function is propagated on a grid with appropriately short time steps. Although the preparation and measurement of arbitrary states on a quantum computer is inefficient, here we demonstrate how to prepare states of chemical interest efficiently. We also show how to efficiently obtain chemically relevant observables, such as state-to-state transition probabilities and thermal reaction rates. Quantum computers using these techniques could outperform current classical computers with 100 qubits.

  6. Dynamic 3-D chemical agent cloud mapping using a sensor constellation deployed on mobile platforms

    Science.gov (United States)

    Cosofret, Bogdan R.; Konno, Daisei; Rossi, David; Marinelli, William J.; Seem, Pete

    2014-05-01

    The need for standoff detection technology to provide early Chem-Bio (CB) threat warning is well documented. Much of the information obtained by a single passive sensor is limited to bearing and angular extent of the threat cloud. In order to obtain absolute geo-location, range to threat, 3-D extent and detailed composition of the chemical threat, fusion of information from multiple passive sensors is needed. A capability that provides on-the-move chemical cloud characterization is key to the development of real-time Battlespace Awareness. We have developed, implemented and tested algorithms and hardware to perform the fusion of information obtained from two mobile LWIR passive hyperspectral sensors. The implementation of the capability is driven by current Nuclear, Biological and Chemical Reconnaissance Vehicle operational tactics and represents a mission focused alternative of the already demonstrated 5-sensor static Range Test Validation System (RTVS).1 The new capability consists of hardware for sensor pointing and attitude information which is made available for streaming and aggregation as part of the data fusion process for threat characterization. Cloud information is generated using 2-sensor data ingested into a suite of triangulation and tomographic reconstruction algorithms. The approaches are amenable to using a limited number of viewing projections and unfavorable sensor geometries resulting from mobile operation. In this paper we describe the system architecture and present an analysis of results obtained during the initial testing of the system at Dugway Proving Ground during BioWeek 2013.

  7. Infrared Chemical Nano-Imaging: Accessing Structure, Coupling, and Dynamics on Molecular Length Scales

    Energy Technology Data Exchange (ETDEWEB)

    Muller, Eric A.; Pollard, Benjamin; Raschke, Markus Bernd

    2015-04-02

    This Perspective highlights recent advances in infrared vibrational chemical nano-imaging. In its implementations of scattering scanning near-field optical microscopy (s-SNOM) and photothermal-induced resonance (PTIR), IR nanospectroscopy provides few-nanometer spatial resolution for the investigation of polymer, biomaterial, and related soft-matter surfaces and nanostructures. Broad-band IR s-SNOM with coherent laser and synchrotron sources allows for chemical recognition with small-ensemble sensitivity and the potential for sensitivity reaching the single-molecule limit. Probing selected vibrational marker resonances, it gives access to nanoscale chemical imaging of composition, domain morphologies, order/disorder, molecular orientation, or crystallographic phases. Local intra- and intermolecular coupling can be measured through frequency shifts of a vibrational marker in heterogeneous environments and associated inhomogeneities in vibrational dephasing. In combination with ultrafast spectroscopy, the vibrational coherent evolution of homogeneous sub-ensembles coupled to their environment can be observed. Outstanding challenges are discussed in terms of extensions to coherent and multidimensional spectroscopies, implementation in liquid and in situ environments, general sample limitations, and engineering s-SNOM scanning probes to better control the nano-localized optical excitation and to increase sensitivity.

  8. Fe/C interactions during SWNT growth with C2 feedstock molecules: A quantum chemical molecular dynamics study.

    Science.gov (United States)

    Zheng, Guishan; Irle, Stephan; Morokuma, Keiji

    2006-05-01

    We are presenting the first quantum chemical molecular dynamics (QM/MD) model simulations for iron catalyzed single-walled carbon nanotube (SWNT) growth based on the density functional tight binding (DFTB) quantum chemical potential. As model systems, open-ended (10,10) armchair tube fragments were selected with 0, 10, and 20 Fe atoms attached in 1,4-positions on the open rims, and ensembles of randomly oriented C2 molecules were included to simulate carbon plasma feedstock molecules. Isokinetic trajectories at 1500 K to 3000 K show that divalent Fe increases the number of coordination partners with carbon and/or Fe, depending on the Fe concentration. Fe/C interactions weaken the tube sidewall due to electron transfer from Fe into antibonding carbon orbitals, and C2 addition occurs mainly in an Fe-C2-Fe bridge addition mechanism, while growth of polyyne chains characteristic for high-temperature carbon systems is suppressed in the presence of Fe on the rims of the growing SWNT. Our findings are the first quantum chemical evidence for the importance of intermetallic interactions during SWNT growth.

  9. Nanostructure-directed chemical sensing: The IHSAB principle and the dynamics of acid/base-interface interaction

    Directory of Open Access Journals (Sweden)

    James L. Gole

    2013-01-01

    Full Text Available Nanostructure-decorated n-type semiconductor interfaces are studied in order to develop chemical sensing with nanostructured materials. We couple the tenets of acid/base chemistry with the majority charge carriers of an extrinsic semiconductor. Nanostructured islands are deposited in a process that does not require self-assembly in order to direct a dominant electron-transduction process that forms the basis for reversible chemical sensing in the absence of chemical-bond formation. Gaseous analyte interactions on a metal-oxide-decorated n-type porous silicon interface show a dynamic electron transduction to and from the interface depending upon the relative strength of the gas and metal oxides. The dynamic interaction of NO with TiO2, SnO2, NiO, CuxO, and AuxO (x >> 1, in order of decreasing acidity, demonstrates this effect. Interactions with the metal-oxide-decorated interface can be modified by the in situ nitridation of the oxide nanoparticles, enhancing the basicity of the decorated interface. This process changes the interaction of the interface with the analyte. The observed change to the more basic oxinitrides does not represent a simple increase in surface basicity but appears to involve a change in molecular electronic structure, which is well explained by using the recently developed IHSAB model. The optical pumping of a TiO2 and TiO2−xNx decorated interface demonstrates a significant enhancement in the ability to sense NH3 and NO2. Comparisons to traditional metal-oxide sensors are also discussed.

  10. Nanostructure-directed chemical sensing: The IHSAB principle and the dynamics of acid/base-interface interaction.

    Science.gov (United States)

    Gole, James L; Laminack, William

    2013-01-01

    Nanostructure-decorated n-type semiconductor interfaces are studied in order to develop chemical sensing with nanostructured materials. We couple the tenets of acid/base chemistry with the majority charge carriers of an extrinsic semiconductor. Nanostructured islands are deposited in a process that does not require self-assembly in order to direct a dominant electron-transduction process that forms the basis for reversible chemical sensing in the absence of chemical-bond formation. Gaseous analyte interactions on a metal-oxide-decorated n-type porous silicon interface show a dynamic electron transduction to and from the interface depending upon the relative strength of the gas and metal oxides. The dynamic interaction of NO with TiO(2), SnO(2), NiO, Cu(x)O, and Au(x)O (x > 1), in order of decreasing acidity, demonstrates this effect. Interactions with the metal-oxide-decorated interface can be modified by the in situ nitridation of the oxide nanoparticles, enhancing the basicity of the decorated interface. This process changes the interaction of the interface with the analyte. The observed change to the more basic oxinitrides does not represent a simple increase in surface basicity but appears to involve a change in molecular electronic structure, which is well explained by using the recently developed IHSAB model. The optical pumping of a TiO(2) and TiO(2-) (x)N(x) decorated interface demonstrates a significant enhancement in the ability to sense NH(3) and NO(2). Comparisons to traditional metal-oxide sensors are also discussed.

  11. Tracking chemicals in products around the world: introduction of a dynamic substance flow analysis model and application to PCBs.

    Science.gov (United States)

    Li, Li; Wania, Frank

    2016-09-01

    Dynamically tracking flows and stocks of problematic chemicals in products (CiPs) in the global anthroposphere is essential to understanding their environmental fates and risks. The complex behavior of CiPs during production, use and waste disposal makes this a challenging task. Here we introduce and describe a dynamic substance flow model, named Chemicals in Products - Comprehensive Anthropospheric Fate Estimation (CiP-CAFE), which facilitates the quantification of time-variant flows and stocks of CiPs within and between seven interconnected world regions and the generation of global scale emission estimates. We applied CiP-CAFE to polychlorinated biphenyls (PCBs), first to evaluate its ability to reproduce previously reported global-scale atmospheric emission inventories and second to illustrate its potential applications and merits. CiP-CAFE quantifies the pathways of PCBs during production, use and waste disposal stages, thereby deducing the temporal evolution of in-use and waste stocks and identifying their long-term final sinks. Time-variant estimates of PCB emissions into air, water and soil can be attributed to different processes and be fed directly into a global fate and transport model. By capturing the international movement of PCBs as technical chemicals, and in products and waste, CiP-CAFE reveals that the extent of global dispersal caused by humans is larger than that occurring in the natural environment. Sensitivity analysis indicates that the model output is most sensitive to the PCB production volume and the lifetime of PCB-containing products, suggesting that a shortening of that lifetime is key to reducing future PCB emissions.

  12. Ethiopian Nationalism: An Ideology to Transcend All Odds Äthiopischer Nationalismus: eine Ideologie zur Überwindung aller Widrigkeiten

    Directory of Open Access Journals (Sweden)

    Belachew Gebrewold

    2009-05-01

    Full Text Available This paper attempts to show how nationalism has served to transcend political, social, economic and cultural challenges in Ethiopia. Nationalists in Ethiopia have attempted to harness national cohesion against threats from both within and outside of Ethiopia. External threats have always provided an opportunity to mobilize the citizens and suppress internal dissent in the name of national identity. This paper discusses different forms of nationalism in Ethiopia and attempts to demonstrate that in the conflict between Eritrea and Ethiopia, though territory and economic issues indeed played a role, to reduce the causes of conflict merely to these two factors is a mistake. This conflict has to be approached from a political-psychological aspect as well. Unless there is a change in the expression of nationalism and in the perception of national identity, it will be difficult to address the dynamic of the Eritrean-Ethiopian border conflict and find lasting solutions. Dieser Aufsatz will aufzeigen, wie Nationalismus dazu nützlich war, politische, soziale, wirtschaftliche und kulturelle Herausforderungen in Äthiopien zu überwinden. Nationalisten in Äthiopien versuchten, sich den nationalen Zusammenhalt gegen interne und externe Bedrohungen zunutze zu machen. Bedrohungen von außen haben stets eine Möglichkeit geboten, die Bürger zu mobilisieren und interne Auseinandersetzungen im Namen der nationalen Identität zu unterdrücken. Der Aufsatz behandelt verschiedene Formen des Nationalismus in Äthiopien und will darlegen, dass im Konflikt zwischen Eritrea und Äthiopien, in dem territoriale und wirtschaftliche Fragen zwar tatsächlich eine Rolle spielten, es gleichwohl falsch ist, die Ursachen des Konflikts allein auf diese beiden Faktoren zu reduzieren. Dieser Konflikt muss ebenso von einer politisch-psychologischen Seite behandelt werden. Ohne einen Wandel der Formen des Nationalismus und der Wahrnehmung der nationalen Identität wird es schwer

  13. Population dynamics of earthworms in relation to soil physico-chemical parameters in agroforestry systems of Mizoram, India.

    Science.gov (United States)

    Lalthanzara, H; Ramanujam, S N; Jha, L K

    2011-09-01

    Earthworm population dynamics was studied in two agroforestry systems in the tropical hilly terrain of Mizoram, north-east India, over a period of 24 months, from July 2002 to June 2004. Two sites of agroforestry situated at Sakawrtuichhun (SKT) and Pachhunga University College (PUC) campus, Aizawl, having pineapple as the main crop, were selected for detail studies on population dynamics. Five of the total twelve species of earthworm reported from the state were recorded in the study sites. The density of earthworm ranged from 6 to 243 ind.m(-2) and biomass from 3.2 - 677.64 g.m(-2) in SKT. Comparatively the density and biomass in PUC, which is at relatively higher altitude were lowerwith a range of 0 to 176 ind.m(-2) and biomass from 0 - 391.36 g.m(-2) respectively. Population dynamics of earthworm was significantly correlated with rainfall and physical characters of the soil. Earthworm biomass was significantly affected by rainfall and moisture content of the soil. The influence of chemical factors was relatively less.

  14. Investigation of Dynamic Multivariate Chemical Process Monitoring%动态多变量过程监控研究

    Institute of Scientific and Technical Information of China (English)

    谢磊; 张建明; 王树青

    2006-01-01

    Chemical process variables are always driven by random noise and disturbances. The closed-loop control yields process measurements that are auto and cross correlated. The influence of auto and cross correlations on statistical process control (SPC) is investigated in detail by Monte Carlo experiments. It is revealed that in the sense of average performance, the false alarms rates (FAR) of principal component analysis (PCA), dynamic PCA are not affected by the time-series structures of process variables. Nevertheless, non-independent identical distribution will cause the actual FAR to deviate from its theoretic value apparently and result in unexpected consecutive false alarms for normal operating process. Dynamic PCA and ARMA-PCA are demonstrated to be inefficient to remove the influences of auto and cross correlations. Subspace identification-based PCA (SI-PCA) is proposed to improve the monitoring of dynamic processes. Through state space modeling, SI-PCA can remove the auto and cross correlations efficiently and avoid consecutive false alarms. Synthetic Monte Carlo experiments and the application in Tennessee Eastman challenge process illustrate the advantages of the proposed approach.

  15. Dynamic Passive Dosing for Studying the Biotransformation of Hydrophobic Organic Chemicals: Microbial Degradation as an Example

    DEFF Research Database (Denmark)

    Smith, Kilian E. C.; Rein, Arno; Trapp, Stefan

    2012-01-01

    and defined dissolved concentration range, and enables high compound turnover even at low concentrations to simplify end point measurement. As a case study, the biodegradation kinetics of two model HOCs by the bacterium Sphingomonas paucimobilis EPA505 were measured at defined dissolved concentrations ranging...... also similar for both PAHs, but decreased by around 2 orders of magnitude with increasing dissolved concentrations. Dynamic passive dosing is a useful tool for measuring biotransformation kinetics at realistically low and defined dissolved HOC concentrations....

  16. Models of disk chemical evolution focusing the pure dynamical radial mixing

    Directory of Open Access Journals (Sweden)

    Re Fiorentin P.

    2012-02-01

    Full Text Available We performed N-body simulations to study the dynamical evolution of a stellar disk inside a Dark Matter (DM halo. Our results evidence how a standard -radially decreasing- metallicity gradient produces a negative vϕ vs. [Fe/H] correlation, similar to that shown by the thin disk stars, while an inverse radial gradient generates a positive rotation-metallicity correlation, as that observed in the old thick population.

  17. Dynamic and Progressive Control of DNA Origami Conformation by Modulating DNA Helicity with Chemical Adducts.

    Science.gov (United States)

    Chen, Haorong; Zhang, Hanyu; Pan, Jing; Cha, Tae-Gon; Li, Shiming; Andréasson, Joakim; Choi, Jong Hyun

    2016-05-24

    DNA origami has received enormous attention for its ability to program complex nanostructures with a few nanometer precision. Dynamic origami structures that change conformation in response to environmental cues or external signals hold great promises in sensing and actuation at the nanoscale. The reconfiguration mechanism of existing dynamic origami structures is mostly limited to single-stranded hinges and relies almost exclusively on DNA hybridization or strand displacement. Here, we show an alternative approach by demonstrating on-demand conformation changes with DNA-binding molecules, which intercalate between base pairs and unwind DNA double helices. The unwinding effect modulates the helicity mismatch in DNA origami, which significantly influences the internal stress and the global conformation of the origami structure. We demonstrate the switching of a polymerized origami nanoribbon between different twisting states and a well-constrained torsional deformation in a monomeric origami shaft. The structural transformation is shown to be reversible, and binding isotherms confirm the reconfiguration mechanism. This approach provides a rapid and reversible means to change DNA origami conformation, which can be used for dynamic and progressive control at the nanoscale.

  18. A Hybrid Improved Genetic Algorithm and Its Application in Dynamic Optimization Problems of Chemical Processes

    Institute of Scientific and Technical Information of China (English)

    SUN Fan; DU Wenli; QI Rongbin; QIAN Feng; ZHONG Weimin

    2013-01-01

    The solutions of dynamic optimization problems are usually very difficult due to their highly nonlinear and multidimensional nature.Genetic algorithm(GA)has been proved to be a feasible method when the gradient is difficult to calculate.Its advantage is that the control profiles at all time stages are optimized simultaneously,but its convergence is very slow in the later period of evolution and it is easily trapped in the local optimum.In this study,a hybrid improved genetic algorithm(HIGA)for solving dynamic optimization problems is proposed to overcome these defects.Simplex method(SM)is used to perform the local search in the neighborhood of the optimal solution.By using SM,the ideal searching direction of global optimal solution could be found as soon as possible and the convergence speed of the algorithm is improved.The hybrid algorithm presents some improvements,such as protecting the best individual,accepting immigrations,as well as employing adaptive crossover and Gaussian mutation operators.The efficiency of the proposed algorithm is demonstrated by solving several dynamic optimization problems.At last,HIGA is applied to the optimal production of secreted protein in a fed batch reactor and the optimal feed-rate found by HIGA is effective and relatively stable.

  19. Complex, dynamic combination of physical, chemical and nutritional variables controls spatio-temporal variation of sandy beach community structure.

    Science.gov (United States)

    Ortega Cisneros, Kelly; Smit, Albertus J; Laudien, Jürgen; Schoeman, David S

    2011-01-01

    Sandy beach ecological theory states that physical features of the beach control macrobenthic community structure on all but the most dissipative beaches. However, few studies have simultaneously evaluated the relative importance of physical, chemical and biological factors as potential explanatory variables for meso-scale spatio-temporal patterns of intertidal community structure in these systems. Here, we investigate macroinfaunal community structure of a micro-tidal sandy beach that is located on an oligotrophic subtropical coast and is influenced by seasonal estuarine input. We repeatedly sampled biological and environmental variables at a series of beach transects arranged at increasing distances from the estuary mouth. Sampling took place over a period of five months, corresponding with the transition between the dry and wet season. This allowed assessment of biological-physical relationships across chemical and nutritional gradients associated with a range of estuarine inputs. Physical, chemical, and biological response variables, as well as measures of community structure, showed significant spatio-temporal patterns. In general, bivariate relationships between biological and environmental variables were rare and weak. However, multivariate correlation approaches identified a variety of environmental variables (i.e., sampling session, the C∶N ratio of particulate organic matter, dissolved inorganic nutrient concentrations, various size fractions of photopigment concentrations, salinity and, to a lesser extent, beach width and sediment kurtosis) that either alone or combined provided significant explanatory power for spatio-temporal patterns of macroinfaunal community structure. Overall, these results showed that the macrobenthic community on Mtunzini Beach was not structured primarily by physical factors, but instead by a complex and dynamic blend of nutritional, chemical and physical drivers. This emphasises the need to recognise ocean-exposed sandy

  20. Complex, Dynamic Combination of Physical, Chemical and Nutritional Variables Controls Spatio-Temporal Variation of Sandy Beach Community Structure

    Science.gov (United States)

    Ortega Cisneros, Kelly; Smit, Albertus J.; Laudien, Jürgen; Schoeman, David S.

    2011-01-01

    Sandy beach ecological theory states that physical features of the beach control macrobenthic community structure on all but the most dissipative beaches. However, few studies have simultaneously evaluated the relative importance of physical, chemical and biological factors as potential explanatory variables for meso-scale spatio-temporal patterns of intertidal community structure in these systems. Here, we investigate macroinfaunal community structure of a micro-tidal sandy beach that is located on an oligotrophic subtropical coast and is influenced by seasonal estuarine input. We repeatedly sampled biological and environmental variables at a series of beach transects arranged at increasing distances from the estuary mouth. Sampling took place over a period of five months, corresponding with the transition between the dry and wet season. This allowed assessment of biological-physical relationships across chemical and nutritional gradients associated with a range of estuarine inputs. Physical, chemical, and biological response variables, as well as measures of community structure, showed significant spatio-temporal patterns. In general, bivariate relationships between biological and environmental variables were rare and weak. However, multivariate correlation approaches identified a variety of environmental variables (i.e., sampling session, the C∶N ratio of particulate organic matter, dissolved inorganic nutrient concentrations, various size fractions of photopigment concentrations, salinity and, to a lesser extent, beach width and sediment kurtosis) that either alone or combined provided significant explanatory power for spatio-temporal patterns of macroinfaunal community structure. Overall, these results showed that the macrobenthic community on Mtunzini Beach was not structured primarily by physical factors, but instead by a complex and dynamic blend of nutritional, chemical and physical drivers. This emphasises the need to recognise ocean-exposed sandy

  1. REPRESENTING AEROSOL DYNAMICS AND PROPERTIES IN CHEMICAL TRANSPORT MODELS BY THE METHOD OF MOMENTS.

    Energy Technology Data Exchange (ETDEWEB)

    SCHWARTZ, S.E.; MCGRAW, R.; BENKOVITZ, C.M.; WRIGHT, D.L.

    2001-04-01

    Atmospheric aerosols, suspensions of solid or liquid particles, are an important multi-phase system. Aerosols scatter and absorb shortwave (solar) radiation, affecting climate (Charlson et al., 1992; Schwartz, 1996) and visibility; nucleate cloud droplet formation, modifying the reflectivity of clouds (Twomey et al., 1984; Schwartz and Slingo, 1996) as well as contributing to composition of cloudwater and to wet deposition (Seinfeld and Pandis, 1998); and affect human health through inhalation (NRC, 1998). Existing and prospective air quality regulations impose standards on concentrations of atmospheric aerosols to protect human health and welfare (EPA, 1998). Chemical transport and transformation models representing the loading and geographical distribution of aerosols and precursor gases are needed to permit development of effective and efficient strategies for meeting air quality standards, and for examining aerosol effects on climate retrospectively and prospectively for different emissions scenarios. Important aerosol properties and processes depend on their size distribution: light scattering, cloud nucleating properties, dry deposition, and penetration into airways of lungs. The evolution of the mass loading itself depends on particle size because of the size dependence of growth and removal processes. For these reasons it is increasingly recognized that chemical transport and transformation models must represent not just the mass loading of atmospheric particulate matter but also the aerosol microphysical properties and the evolution of these properties if aerosols are to be accurately represented in these models. If the size distribution of the aerosol is known, a given property can be evaluated as the integral of the appropriate kernel function over the size distribution. This has motivated the approach of determining aerosol size distribution, and of explicitly representing this distribution and its evolution in chemical transport models.

  2. “A thrilling beauty”?: Violence, Transcendence and the Shankill Butchers in Eoin McNamee’s Resurrection Man

    Directory of Open Access Journals (Sweden)

    Billy Gray

    2014-03-01

    Full Text Available The Shankill Butchers, a small group of UVF members based in the Shankill Road during the 1970s, acquired a reputation for indulging in pathological violence to a degree hitherto unparalleled in the annals of “Troubles”-related murders. Eoin McNamee’s Resurrection Man has been accorded a great degree of critical attention regarding the contentious manner in which it has attempted to investigate the Shankill Butchers’ legacy. My article attempts to suggest that the novel’s metafictive universe and innovative generic hybridity represent an attempt to transcend the spatial borders of Northern Ireland in order to present the conflict as an allegory of existential, postmodern alienation. The violent psychopathology of the Shankill Butchers is, in McNamee’s text, of universal as opposed to local significance, and violence is controversially portrayed as a search for intimacy and transcendence in a world defined by virtual reality.

  3. Transcending the slow bimolecular recombination in lead-halide perovskites for electroluminescence

    Science.gov (United States)

    Xing, Guichuan; Wu, Bo; Wu, Xiangyang; Li, Mingjie; Du, Bin; Wei, Qi; Guo, Jia; Yeow, Edwin K. L.; Sum, Tze Chien; Huang, Wei

    2017-01-01

    The slow bimolecular recombination that drives three-dimensional lead-halide perovskites' outstanding photovoltaic performance is conversely a fundamental limitation for electroluminescence. Under electroluminescence working conditions with typical charge densities lower than 1015 cm−3, defect-states trapping in three-dimensional perovskites competes effectively with the bimolecular radiative recombination. Herein, we overcome this limitation using van-der-Waals-coupled Ruddlesden-Popper perovskite multi-quantum-wells. Injected charge carriers are rapidly localized from adjacent thin few layer (n≤4) multi-quantum-wells to the thick (n≥5) multi-quantum-wells with extremely high efficiency (over 85%) through quantum coupling. Light emission originates from excitonic recombination in the thick multi-quantum-wells at much higher decay rate and efficiency than bimolecular recombination in three-dimensional perovskites. These multi-quantum-wells retain the simple solution processability and high charge carrier mobility of two-dimensional lead-halide perovskites. Importantly, these Ruddlesden-Popper perovskites offer new functionalities unavailable in single phase constituents, permitting the transcendence of the slow bimolecular recombination bottleneck in lead-halide perovskites for efficient electroluminescence. PMID:28239146

  4. A differential equation for Lerch's transcendent and associated symmetric operators in Hilbert space

    Energy Technology Data Exchange (ETDEWEB)

    Kaplitskii, V M [Southern Federal University, Rostov-on-Don (Russian Federation)

    2014-08-01

    The function Ψ(x,y,s)=e{sup iy}Φ(−e{sup iy},s,x), where Φ(z,s,v) is Lerch's transcendent, satisfies the following two-dimensional formally self-adjoint second-order hyperbolic differential equation, where s=1/2+iλ. The corresponding differential expression determines a densely defined symmetric operator (the minimal operator) on the Hilbert space L{sub 2}(Π), where Π=(0,1)×(0,2π). We obtain a description of the domains of definition of some symmetric extensions of the minimal operator. We show that formal solutions of the eigenvalue problem for these symmetric extensions are represented by functional series whose structure resembles that of the Fourier series of Ψ(x,y,s). We discuss sufficient conditions for these formal solutions to be eigenfunctions of the resulting symmetric differential operators. We also demonstrate a close relationship between the spectral properties of these symmetric differential operators and the distribution of the zeros of some special analytic functions analogous to the Riemann zeta function. Bibliography: 15 titles.

  5. NATO Advanced Research Workshop on Painlevé Transcendents, their Asymptotics and Physical Applications

    CERN Document Server

    Winternitz, Pavel; Painlevé Transcendents, their Asymptotics and Physical Applications

    1992-01-01

    The NATO Advanced Research Workshop "Painleve Transcendents, their Asymp­ totics and Physical Applications", held at the Alpine Inn in Sainte-Adele, near Montreal, September 2 -7, 1990, brought together a group of experts to discuss the topic and produce this volume. There were 41 participants from 14 countries and 27 lectures were presented, all included in this volume. The speakers presented reviews of topics to which they themselves have made important contributions and also re­ sults of new original research. The result is a volume which, though multiauthored, has the character of a monograph on a single topic. This is the theory of nonlinear ordinary differential equations, the solutions of which have no movable singularities, other than poles, and the extension of this theory to partial differential equations. For short we shall call such systems "equations with the Painleve property". The search for such equations was a very topical mathematical problem in the 19th century. Early work concent...

  6. Transcendence, religion and spirituality in medicine: Medical students' point of view.

    Science.gov (United States)

    Rassoulian, Anahita; Seidman, Charles; Löffler-Stastka, Henriette

    2016-09-01

    To explore how medical students-the doctors of tomorrow-reflect upon meeting the spiritual needs of their patients, and whether they have reflected on their own religious or spiritual beliefs, or not. The study also investigates to what extent the students feel comfortable with addressing spiritual issues in their patient care, and whether they feel this is beyond their role as medical doctors.A self-administered questionnaire was developed. The survey was administered in teaching classes at the medical university of Vienna. One thousand four hundred (836 women and 564 men) students responded, laying the foundation for a thorough statistical analysis.59.5% of the students had reflected on their own belief concepts, 21.9% consider themselves religious, and 20.1% see themselves as spiritual individuals. 75.6% of the students agreed with the statement that religious conviction/spirituality might have an effect on how cancer patients cope. 85.9% would consider talking with their patients about religious/spiritual issues if patients wish to do so. 86.3% would involve chaplains if they feel it is necessary.The results of this study suggest that future doctors want to see the patient in a wider scope than the bio-psycho-social one, by including the meta-dimension of transcendence.

  7. Human object-similarity judgments reflect and transcend the primate-IT object representation

    Directory of Open Access Journals (Sweden)

    Marieke eMur

    2013-03-01

    Full Text Available Primate inferior temporal (IT cortex is thought to contain a high-level representation of objects at the interface between vision and semantics. This suggests that the perceived similarity of real-world objects might be predicted from the IT representation. Here we show that objects that elicit similar activity patterns in human IT tend to be judged as similar by humans. The IT representation explained the human judgments better than early visual cortex, other ventral stream regions, and a range of computational models. Human similarity judgments exhibited category clusters that reflected several categorical divisions that are prevalent in the IT representation of both human and monkey, including the animate/inanimate and the face/body division. Human judgments also reflected the within-category representation of IT. However, the judgments transcended the IT representation in that they introduced additional categorical divisions. In particular, human judgments emphasized human-related additional divisions between human and nonhuman animals and between man-made and natural objects. Human IT was more similar to monkey IT than to human judgments. One interpretation is that IT has evolved visual feature detectors that distinguish between animates and inanimates and between faces and bodies because these divisions are fundamental to survival and reproduction for all primate species, and that other brain systems serve to more flexibly introduce species-dependent and evolutionarily more recent divisions.

  8. Default mode network activation and Transcendental Meditation practice: Focused Attention or Automatic Self-transcending?

    Science.gov (United States)

    Travis, Frederick; Parim, Niyazi

    2017-02-01

    This study used subjective reports and eLORETA analysis to assess to what extent Transcendental Meditation (TM) might involve focused attention-voluntary control of mental content. Eighty-seven TM subjects with one month to five years TM experience participated in this study. Regression analysis of years TM practice and self-reported transcendental experiences (lack of time, space and body sense) during meditation practice was flat (r=.07). Those practicing Transcendental Meditation for 1month reported as much transcending as those with 5years of practice. The eLORETA comparison of eyes-closed rest/task and TM practice/task identified similar areas of activation: theta and alpha activation during rest and TM in the posterior cingulate and precuneus, part of the default mode network, and beta2 and beta3 activation during the task in anterior cingulate, ventral lateral and dorsolateral prefrontal cortices, part of the central executive network. In addition, eLORETA comparison of rest and TM identified higher beta temporal activation during rest and higher theta orbitofrontal activation during TM. Thus, it does not seem accurate to include TM practice with meditations in the catgory of Focused Attention, which are characterized by gamma EEG and DMN deactivation. Mixing meditations with different procedures into a single study confounds exploration of meditation effects and confounds application of meditation practices to different subject populations. Copyright © 2016 Elsevier Inc. All rights reserved.

  9. Transcending the slow bimolecular recombination in lead-halide perovskites for electroluminescence.

    Science.gov (United States)

    Xing, Guichuan; Wu, Bo; Wu, Xiangyang; Li, Mingjie; Du, Bin; Wei, Qi; Guo, Jia; Yeow, Edwin K L; Sum, Tze Chien; Huang, Wei

    2017-02-27

    The slow bimolecular recombination that drives three-dimensional lead-halide perovskites' outstanding photovoltaic performance is conversely a fundamental limitation for electroluminescence. Under electroluminescence working conditions with typical charge densities lower than 10(15) cm(-3), defect-states trapping in three-dimensional perovskites competes effectively with the bimolecular radiative recombination. Herein, we overcome this limitation using van-der-Waals-coupled Ruddlesden-Popper perovskite multi-quantum-wells. Injected charge carriers are rapidly localized from adjacent thin few layer (n≤4) multi-quantum-wells to the thick (n≥5) multi-quantum-wells with extremely high efficiency (over 85%) through quantum coupling. Light emission originates from excitonic recombination in the thick multi-quantum-wells at much higher decay rate and efficiency than bimolecular recombination in three-dimensional perovskites. These multi-quantum-wells retain the simple solution processability and high charge carrier mobility of two-dimensional lead-halide perovskites. Importantly, these Ruddlesden-Popper perovskites offer new functionalities unavailable in single phase constituents, permitting the transcendence of the slow bimolecular recombination bottleneck in lead-halide perovskites for efficient electroluminescence.

  10. Human Object-Similarity Judgments Reflect and Transcend the Primate-IT Object Representation.

    Science.gov (United States)

    Mur, Marieke; Meys, Mirjam; Bodurka, Jerzy; Goebel, Rainer; Bandettini, Peter A; Kriegeskorte, Nikolaus

    2013-01-01

    Primate inferior temporal (IT) cortex is thought to contain a high-level representation of objects at the interface between vision and semantics. This suggests that the perceived similarity of real-world objects might be predicted from the IT representation. Here we show that objects that elicit similar activity patterns in human IT (hIT) tend to be judged as similar by humans. The IT representation explained the human judgments better than early visual cortex, other ventral-stream regions, and a range of computational models. Human similarity judgments exhibited category clusters that reflected several categorical divisions that are prevalent in the IT representation of both human and monkey, including the animate/inanimate and the face/body division. Human judgments also reflected the within-category representation of IT. However, the judgments transcended the IT representation in that they introduced additional categorical divisions. In particular, human judgments emphasized human-related additional divisions between human and non-human animals and between man-made and natural objects. hIT was more similar to monkey IT than to human judgments. One interpretation is that IT has evolved visual-feature detectors that distinguish between animates and inanimates and between faces and bodies because these divisions are fundamental to survival and reproduction for all primate species, and that other brain systems serve to more flexibly introduce species-dependent and evolutionarily more recent divisions.

  11. Self-transcending meditation is good for mental health: why this should be the case.

    Science.gov (United States)

    Hankey, Alex; Shetkar, Rashmi

    2016-06-01

    A simple theory of health has recently been proposed: while poor quality regulation corresponds to poor quality health so that improving regulation should improve health, optimal regulation optimizes function and optimizes health. Examining the term 'optimal regulation' in biological systems leads to a straightforward definition in terms of 'criticality' in complexity biology, a concept that seems to apply universally throughout biology. Criticality maximizes information processing and sensitivity of response to external stimuli, and for these reasons may be held to optimize regulation. In this way a definition of health has been given in terms of regulation, a scientific concept, which ties into detailed properties of complex systems, including brain cortices, and mental health. Models of experience and meditation built on complexity also point to criticality: it represents the condition making self-awareness possible, and is strengthened by meditation practices leading to the state of pure consciousness-the content-free state of mind in deep meditation. From this it follows that healthy function of the brain cortex, its sensitivity,y and consistency of response to external challenges should improve by practicing techniques leading to content-free awareness-transcending the original focus introduced during practice. Evidence for this is reviewed.

  12. Are ACE-inhibitors or ARB's still needed for cardiovascular prevention in high risk patients? Insights from profess and transcend.

    Science.gov (United States)

    Van Mieghem, W; Billiouw, J M; Brohet, C; Dupont, A G; Gazagnes, M D; Heller, F; Krzesinski, J M; Missault, L; Persu, A; Piérard, L; Rottiers, R; Vanhooren, G; Vervaet, P; Herman, A G

    2010-01-01

    The HOPE and EUROPA clinical studies have shown that treatment with the angiotensin-converting enzyme (ACE) inhibitors, ramipril and perindopril, may reduce the occurrence of major cardiovascular events in patients with proven atherosclerotic disease. The recently published results of the PRoFESS and TRANSCEND trials completed the much needed information concerning the use of an angiotensin receptor blocker for patients at high risk of cardiovascular events. PROFESS compared a therapy of telmisartan 80 mg daily with placebo in patients with a recent ischemic stroke. The difference in the primary outcome of first recurrent stroke was not statistically significant between telmisartan and placebo. The secondary outcome of major cardiovascular events showed a relative risk reduction (RRR) of 7% in favour of telmisartan. This tended to be significant (p = 0.06) despite a rather short follow-up period of only 28 months. In TRANSCEND 5926 patients at high risk for cardiovascular events were randomized to a treatment with telmisartan 80 mg daily or placebo for a mean duration of follow-up of 56 months. The primary composite outcome of cardiovascular death, myocardial infarction, stroke or hospitalization for heart failure showed a non-significant 8% RRR in favour of the telmisartan treated patients. The main secondary outcome of cardiovascular death and myocardial infarction or stroke as used in the HOPE trial showed a non-significant RRR of 13% in favour of telmisartan treated patients (p = 0.068 adjusted for multiplicity of comparisons). In comparing the Kaplan-Meier curves for the endpoint of major cardiovascular events used in HOPE, EUROPA, TRANSCEND and PRoFESS, the trends are similar. Results of most of the recently published trials have been neutral.This could partly be explained by major improvements in the optimal background therapy of the patients included. Nevertheless, the results of PRoFESS and TRANSCEND do not contradict the results from previous studies with

  13. God, Moses and Levinas: On being the other and relating to the other. A perspective on transcendence from religious experience

    Directory of Open Access Journals (Sweden)

    D.P. Veldsman

    2012-02-01

    Full Text Available

    Within the context of religious experience, understood as testimony to transcendence (Stoker, this article focus on a specific constitutive element thereof, namely intentionality. It is discussed as concept in relation to three other concepts, namely religious experience, experience and transcendence. To elaborate on the importance of the qualification of the concept of intentionality, three conversation partners are engaged. The French Jewish philosopher and Talmudic commentator Emmanuel Levinas (1906-1995 since his view point on “The (Oother” makes the concept of “transcendence” problematic in a very insightful manner. The Dutch philosopher of religion Wessel Stoker and his proposal for “trans-intentionality” as a constitutive element of religious experience, and the experience of Moses with God as narrated in Ex 3. The contributions on transcendence by Levinas and Stoker are finally critically evaluated in relation to the Moses experience.

    And God said to Moses: “I will be who I will be” (Ex 3:14

    For if God is God, then it is impossible for God to be given in any intuition orphenomenal experience, to be contained by any concept governed by any principal. But it is this very impossibility – this infinity and incomprehensibility – that makes God “possible” as God. God alone lets God self be defined by indefinable impossibility, for God begins where human possibility ends. What is impossible for us is precisely God’s characteristic possibility, for with God nothing is impossible (Jean-Luc Marion

    Divinity is not transcendent (“wholly other”, but incarnate; and the incarnation, the event “inaugurating the dissolution of divine transcendence” (Gianni Vattimo.

  14. Dynamics of chemically stressed populations: the deduction of population consequences from effects on individuals

    Energy Technology Data Exchange (ETDEWEB)

    Kooijman, S.A.; Metz, J.A.

    1984-06-01

    A general, simple, and explicit model for the age-dependent growth and reproduction of individuals as a function of food supply is presented. The model assumes a Holling-type functional response coupled with a von Bertalanffy body growth law, a fixed ratio between the energy utilized for reproduction and respiration, and a juvenile stage that ends as soon as the animal attains a sufficient weight. This model is shown to fit the available data on the development of Daphnia magna quite well. The model is used as a basis for studying the effects of chemicals on population growth rate, given the effects on individuals. Effects on individual growth and reproduction are reflected in a concentration-dependent relative reduction of the population growth rate. Effects on feeding rate, digestion, basal metabolism, and survival work out much more dramatically at low natural population growth rates. This already follows from a much simpler model that assumes age-independent reproduction, as exemplified to a good approximation by the rotifer Brachionus rubens. The theoretical results are supplemented with experimental evidence, implying that the stress on a population at a certain concentration of a chemical may indeed be strongly dependent on the feeding state of that population.

  15. How effective leaders achieve success in critical change initiatives, Part 2: why change leadership must transcend project management for complex initiatives to be successful.

    Science.gov (United States)

    King, Sharon; Peterson, Larry

    2007-01-01

    This article is the second in a series outlining how effective leaders achieve success in critical change initiatives. This article focuses on why change leadership must transcend project management for complex initiatives to be successful.

  16. Mechanism resulting in chemical imbalance due to cellular damage associated with mechanoporation: A molecular dynamics study

    Science.gov (United States)

    Sliozberg, Yelena R.; Chantawansri, Tanya L.

    2016-05-01

    To elucidate the mechanism of ion transport through a transmembrane pore, all-atom molecular dynamics simulations were employed. A model membrane where a pore connects the intra- and extra-cellular compartment was considered. Pores with radii of 1.5 nm or less exhibited resealing over the course of 135 ns simulations, and ionic disturbance is minimal. Ion transport through a larger pore (2 nm radius) leads to a substantial change in the intra- and extra-cellular ionic concentrations. The influx of Na+ and Cl- ions down their concentration gradients is greater than the efflux of K+ leading to an osmotic influx of water.

  17. Closed Loop Adaptive Refinement of Dynamical Models for Complex Chemical Reactions

    Science.gov (United States)

    2008-06-26

    CH3Br, Ar + H2O are given below. 3.1 Cl− + CH3Br Reaction A global RS-HDMR input/output map for the SN2 reaction Cl− +CH3Br→ ClCH3 +Br − (9) 3 was...2257-2266. [16] Wang H. B., Hase W. L. (1996). Reaction path Hamiltonian analysis of the dynamics for Cl− + CH3Br→ ClCH3 + Br − SN2 nucleophilic... reaction Cl − + CH3Br → ClCH3 + Br −, J. Chem. Phys., 111(24), 10887- 10894. [18] Sun, L., Hase, W. L., Song, K. (2001). Trajectory studies of SN2

  18. Decomposition Dynamics and Changes in Chemical Composition of Wheat Straw Residue under Anaerobic and Aerobic Conditions.

    Science.gov (United States)

    Gao, Hongjian; Chen, Xi; Wei, Junling; Zhang, Yajie; Zhang, Ligan; Chang, Jiang; Thompson, Michael L

    2016-01-01

    Soil aeration is a crucial factor that regulates crop residue decomposition, and the chemical composition of decomposing crop residues may change the forms and availability of soil nutrients, such as N and P. However, to date, differences in the chemical composition of crop straw residues after incorporation into soil and during its decomposition under anaerobic vs. aerobic conditions have not been well documented. The objective of the present study was to assess changes in the C-containing functional groups of wheat straw residue during its decomposition in anaerobic and aerobic environments. A 12-month incubation experiment was carried out to investigate the temporal variations of mass, carbon, and nitrogen loss, as well as changes in the chemical composition of wheat (Triticum aestivum L) straw residues under anaerobic and aerobic conditions by measuring C-containing functional groups using solid state nuclear magnetic resonance (NMR) spectroscopy. The residual mass, carbon content, and nitrogen content of the straw residue sharply declined during the initial 3 months, and then slowly decreased during the last incubation period from 3 to 12 months. The decomposition rate constant (k) for mass loss under aerobic conditions (0.022 d-1) was higher than that under anaerobic conditions (0.014 d-1). The residual mass percentage of cellulose and hemicellulose in the wheat straw gradually declined, whereas that of lignin gradually increased during the entire 12-month incubation period. The NMR spectra of C-containing functional groups in the decomposing straw under both aerobic and anaerobic conditions were similar at the beginning of the incubation as well as at 1 month, 6 months, and 12 months. The main alterations in C-containing functional groups during the decomposition of wheat straw were a decrease in the relative abundances of O-alkyl C and an increase in the relative abundances of alkyl C, aromatic C and COO/N-C = O functional groups. The NMR signals of alkyl C

  19. Synthesis of Formamide and Related Organic Species in the Interstellar Medium via Chemical Dynamics Simulations

    Science.gov (United States)

    Spezia, Riccardo; Jeanvoine, Yannick; Hase, William L.; Song, Kihyung; Largo, Antonio

    2016-08-01

    We show, by means of direct dynamics simulations, how it is possible to define possible reactants and mechanisms leading to the formation of formamide in the interstellar medium. In particular, different ion-molecule reactions in the gas phase were considered: NH3OH+, NH2OH{}2+, H2COH+, and NH4 + for the ions and NH2OH, H2CO, and NH3 for the partner neutrals. These calculations were combined with high level ab initio calculations to investigate possible further evolution of the products observed. In particular, for formamide, we propose that the NH2OH{}2+ + H2CO reaction can produce an isomer, NH2OCH{}2+, that, after dissociative recombination, can produce neutral formamide, which was observed in space. The direct dynamics do not pre-impose any reaction pathways and in other reactions, we did not observe the formation of formamide or any possible precursor. On the other hand, we obtained other interesting reactions, like the formation of NH2CH{}2+. Finally, some radiative association processes are proposed. All of the results obtained are discussed in light of the species observed in radioastronomy.

  20. Molecules in Motion: Chemical Reaction and Allied Dynamics in Solution and Elsewhere

    Science.gov (United States)

    Hynes, James T.

    2015-04-01

    After my acceptance of the kind invitation from Todd Martínez and Mark Johnson, Co-Editors of this journal, to write this article, I had to decide just how to actually do this, given the existence of a fairly personal and extended autobiographical account of recent vintage detailing my youth, education, and assorted experiences and activities at the University of Colorado, Boulder, and later also at Ecole Normale Supérieure in Paris ( 1 ). In the end, I settled on a differently styled recounting of the adventures with my students, postdocs, collaborators, and colleagues in trying to unravel, comprehend, describe, and occasionally even predict the manifestations and consequences of the myriad assortment of molecular dances that contribute to and govern the rates and mechanisms of chemical reactions in solution (and elsewhere). The result follows.

  1. Plasmonic hot carrier dynamics in solid-state and chemical systems for energy conversion

    Science.gov (United States)

    Narang, Prineha; Sundararaman, Ravishankar; Atwater, Harry A.

    2016-06-01

    Surface plasmons provide a pathway to efficiently absorb and confine light in metallic nanostructures, thereby bridging photonics to the nano scale. The decay of surface plasmons generates energetic `hot' carriers, which can drive chemical reactions or be injected into semiconductors for nano-scale photochemical or photovoltaic energy conversion. Novel plasmonic hot carrier devices and architectures continue to be demonstrated, but the complexity of the underlying processes make a complete microscopic understanding of all the mechanisms and design considerations for such devices extremely challenging.Here,we review the theoretical and computational efforts to understand and model plasmonic hot carrier devices.We split the problem into three steps: hot carrier generation, transport and collection, and review theoretical approaches with the appropriate level of detail for each step along with their predictions.We identify the key advances necessary to complete the microscopic mechanistic picture and facilitate the design of the next generation of devices and materials for plasmonic energy conversion.

  2. Chemical characterization and dynamics of particulate combined amino acids in Pacific surface waters

    Science.gov (United States)

    Tsukasaki, Ayumi; Tanoue, Eiichiro

    2010-01-01

    Particulate organic matter (POM) in surface water plays an essential role in maintaining marine ecosystem and is a complex mixture of living POM (organisms) and non-living POM (detritus). Transformation of organic constituents of organisms to detritus may be the most active part in the decomposition processes of organic matter in marine biogeochemistry. Distribution and chemical fractionation of particulate combined amino acids (PCAAs) in surface waters from Southern Ocean to tropical waters along a transect of 170°W were examined to clarify the transfer processes of organic constituents of organisms to detritus. The observational facts may be summarized as follows. 1) Degradation Index (DI) based on principal component analysis of amino acid composition of bulk PCAAs agreed with the traditional degradation indicators of bulk POM, i.e., PCAAs-carbon (C)/particulate organic carbon (POC), PCAAs-nitrogen (N)/particulate nitrogen (PN) and C/N. 2) PCAAs were distinguished into 3 fractions, i.e., Urea-soluble, Sodium Dodecyl Sulfate (SDS)-soluble and SDS/Urea-insoluble fractions, by means of solubility against reagents frequently used for protein extraction from biological samples. Proportions of PCAAs of the 3 fractions to bulk PCAAs were almost constant, although concentrations of the PCAAs of 3 fractions as well as bulk in seawater varied two orders of magnitude over the transect. 3) There was no significant difference among DI values of the 3 fractions, although molecular mass distributions of the Urea-soluble and SDS-soluble fractions determined by SDS-polyacrylamide gel electrophoresis were different. The results indicated that no one fraction was particularly susceptible to degradation and that there is a common mechanism for transferring and maintaining the similar chemical quality of bulk POM over the transect.

  3. Chemical evolution of the Salton Sea, California: Nutrient and selenium dynamics

    Science.gov (United States)

    Schroeder, R.A.; Orem, W.H.; Kharaka, Y.K.

    2002-01-01

    The Salton Sea is a 1000-km2 terminal lake located in the desert area of southeastern California. This saline (???44 000 mg l-1 dissolved solids) lake started as fresh water in 1905-07 by accidental flooding of the Colorado River, and it is maintained by agricultural runoff of irrigation water diverted from the Colorado River. The Salton Sea and surrounding wetlands have recently acquired substantial ecological importance because of the death of large numbers of birds and fish, and the establishment of a program to restore the health of the Sea. In this report, we present new data on the salinity and concentration of selected chemicals in the Salton Sea water, porewater and sediments, emphasizing the constituents of concern: nutrients (N and P), Se and salinity. Chemical profiles from a Salton Sea core estimated to have a sedimentation rate of 2.3 mm yr-1 show increasing concentrations of OC, N, and P in younger sediment that are believed to reflect increasing eutrophication of the lake. Porewater profiles from two locations in the Sea show that diffusion from bottom sediment is only a minor source of nutrients to the overlying water as compared to irrigation water inputs. Although loss of N and Se by microbial-mediated volatilization is possible, comparison of selected element concentrations in river inputs and water and sediments from the Salton Sea indicates that most of the N (from fertilizer) and virtually all of the Se (delivered in irrigation water from the Colorado River) discharged to the Sea still reside within its bottom sediment. Laboratory simulation on mixtures of sediment and water from the Salton Sea suggest that sediment is a potential source of N and Se to the water column under aerobic conditions. Hence, it is important that any engineered changes made to the Salton Sea for remediation or for transfer of water out of the basin do not result in remobilization of nutrients and Se from the bottom sediment into the overlying water.

  4. Adsorption properties and degradation dynamics of endocrine-disrupting chemical levonorgestrel in soils.

    Science.gov (United States)

    Tang, Tao; Shi, Tianyu; Li, Deguang; Xia, Jinming; Hu, Qiongbo; Cao, Yongsong

    2012-04-25

    Levonorgestrel, a synthetic progesterone used as an oral contraceptive or emergency contraceptive pill, has been shown to be an endocrine-disrupting chemical. To assess the environmental risk of levonorgestrel, batch experiments and laboratory microcosm studies were conducted to investigate the adsorption and degradation of levonorgestrel in five contrasting soils of China. Freundlich and Langmuir models were applied to sorption data to examine the affinity of levonorgestrel for soils with varying physical and chemical properties. The K(f) of levonorgestrel in the tested soils ranged from 10.79 to 60.92 mg(1-n) L(n) kg(-1) with N between 0.69 and 1.23, and the Q(m) ranged from 18.18 to 196.08 mg/kg. The multiple regression analysis was conducted between K(f) and soil properties. Results indicate that total organic carbon plays a dominant role in the adsorption process. Gibbs free energy values less than 40 kJ/mol demonstrate that levonorgestrel sorption on soils could be considered as a physical adsorption. The degradation of levonorgestrel in five soils was fitted by the first-order reaction kinetics model. The half-lives of levonorgestrel were between 4.32 and 11.55 days. The initial concentration and sterilization experiments illustrated that the degradation rate of levonorgestrel in soil was concentration-dependent and microbially mediated. The low mobility potential of levonorgestrel in soils was predicted by the groundwater ubiquity score (GUS) and retardation factor (R(f)).

  5. The role of normally hyperbolic invariant manifolds (NHIMS) in the context of the phase space setting for chemical reaction dynamics

    Science.gov (United States)

    Wiggins, Stephen

    2016-11-01

    In this paper we give an introduction to the notion of a normally hyperbolic invariant manifold (NHIM) and its role in chemical reaction dynamics.We do this by considering simple examples for one-, two-, and three-degree-of-freedom systems where explicit calculations can be carried out for all of the relevant geometrical structures and their properties can be explicitly understood. We specifically emphasize the notion of a NHIM as a "phase space concept". In particular, we make the observation that the (phase space) NHIM plays the role of "carrying" the (configuration space) properties of a saddle point of the potential energy surface into phase space. We also consider an explicit example of a 2-degree-of-freedom system where a "global" dividing surface can be constructed using two index one saddles and one index two saddle. Such a dividing surface has arisen in several recent applications and, therefore, such a construction may be of wider interest.

  6. Novel Control Vector Parameterization Method with Differential Evolution Algorithm and Its Application in Dynamic Optimization of Chemical Processes

    Institute of Scientific and Technical Information of China (English)

    SUN Fan; ZHONG Weimin; CHENG Hui; QIAN Feng

    2013-01-01

    Two general approaches are adopted in solving dynamic optimization problems in chemical processes,namely,the analytical and numerical methods.The numerical method,which is based on heuristic algorithms,has been widely used.An approach that combines differential evolution (DE) algorithm and control vector parameterization (CVP) is proposed in this paper.In the proposed CVP,control variables are approximated with polynomials based on state variables and time in the entire time interval.Region reduction strategy is used in DE to reduce the width of the search region,which improves the computing efficiency.The results of the case studies demonstrate the feasibility and efficiency of the proposed methods.

  7. Chemical imaging of molecular changes in a hydrated single cell by dynamic secondary ion mass spectrometry and super-resolution microscopy

    Energy Technology Data Exchange (ETDEWEB)

    Hua, Xin; Szymanski, Craig J.; Wang, Zhaoying; Zhou, Yufan; Ma, Xiang; Yu, Jiachao; Evans, James E.; Orr, Galya; Liu, Songqin; Zhu, Zihua; Yu, Xiao-Ying

    2016-05-15

    Chemical imaging of single cells is important in capturing biological dynamics. Single cell correlative imaging is realized between structured illumination microscopy (SIM) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) using System for Analysis at the Liquid Vacuum Interface (SALVI), a multimodal microreactor. SIM characterized cells and guided subsequent ToF-SIMS analysis. Dynamic ToF-SIMS provided time- and space-resolved cell molecular mapping. Lipid fragments were identified in the hydrated cell membrane. Principal component analysis was used to elucidate chemical component differences among mouse lung cells that uptake zinc oxide nanoparticles. Our results provided submicron chemical spatial mapping for investigations of cell dynamics at the molecular level.

  8. Kinetics of SiHCl3 chemical vapor deposition and fluid dynamic simulations.

    Science.gov (United States)

    Cavallotti, Carlo; Masi, Maurizio

    2011-09-01

    Though most of the current silicon photovoltaic technology relies on trichlorosilane (SiHCl3) as a precursor gas to deposit Si, only a few studies have been devoted to the investigation of its gas phase and surface kinetics. In the present work we propose a new kinetic mechanism apt to describe the gas phase and surface chemistry active during the deposition of Si from SiHCl3. Kinetic constants of key reactions were either taken from the literature or determined through ab initio calculations. The capability of the mechanism to reproduce experimental data was tested through the implementation of the kinetic scheme in a fluid dynamic model and in the simulation of both deposition and etching of Si in horizontal reactors. The results of the simulations show that the reactivity of HCl is of key importance in order to control the Si deposition rate. When HCl reaches a critical concentration in the gas phase it starts etching the Si surface, so that the net deposition rate is the net sum of the adsorption rate of the gas phase precursors and the etching rate due to HCl. In these conditions the possibility to further deposit Si is directly related to the rate of consumption of HCl through its reaction with SiHCl3 to give SiCl4. The proposed reaction mechanism was implemented in a 3D fluid dynamic model of a simple Siemens reactor. The simulation results indicate that the proposed interpretation of the growth process applies also to this class of reactors, which operate in what can be defined as a mixed kinetic-transport controlled regime.

  9. Dynamics of phytoplankton in relation to physico-chemical factors of Almatti reservoir of Bijapur District, Karnataka State.

    Science.gov (United States)

    Hulyal, S B; Kaliwal, B B

    2009-06-01

    The present investigation deals with limnobiotic status of the Almatti reservoir from February, 2003 to January, 2005. The study revealed that there exists a fluctuations of the physical factors viz., rainfall, humidity, air and water temperature, pH and electrical conductivity (EC), and chemical factors viz., dissolved oxygen (DO), free carbon dioxide, total alkalinity, total hardness, calcium, magnesium, chloride, nitrate, phosphate, sulphate, bicarbonate and total dissolved solids (TDS). From the data it was also apparent that correlations between the physico-chemical factors and dynamics of phytoplankton could be seen. The simple correlation coefficient test revealed that the cyanophytes number was positively correlated with DO, nitrate, phosphate and negatively significant with total hardness, total alkalinity, EC, calcium, magnesium, sulphate, bicarbonate and TDS. They are inversely correlated with pH, chloride, rainfall and humidity. Bacillariphyceae are correlated with total alkalinity, bicarbonates, magnesium and TDS, whereas inverse correlation was found with rainfall, humidity, pH and phosphate. Desmids showed positive correlation with nitrates, while it was inversely correlated with chloride, rainfall and humidity. Dinophytes density was positively correlated with total alkalinity, EC, total hardness, calcium, bicarbonate, while it showed inverse correlation with rainfall, humidity and phosphate. However, it is obvious that the absence of significant difference between sampling stations for all these parameters in the Almatti reservoir indicated fairly homogeneous conditions and the water quality is also found to be homogeneous.

  10. Effects of Graphene Oxide and Chemically-Reduced Graphene Oxide on the Dynamic Mechanical Properties of Epoxy Amine Composites

    Directory of Open Access Journals (Sweden)

    Cristina Monteserín

    2017-09-01

    Full Text Available Composites based on epoxy/graphene oxide (GO and epoxy/reduced graphene oxide (rGO were investigated for thermal-mechanical performance focusing on the effects of the chemical groups present on nanoadditive-enhanced surfaces. GO and rGO obtained in the present study have been characterized by Fourier transform infrared spectroscopy (FTIR, X-ray photoelectron spectroscopy (XPS, and X-ray powder diffraction (XRD demonstrating that materials with different oxidation degrees have been obtained. Thereafter, GO/epoxy and rGO/epoxy nanocomposites were successfully prepared and thoroughly characterized by dynamic mechanical thermal analysis (DMTA and transmission electron microscopy (TEM. A significant increase in the glass transition temperature was found in comparison with the neat epoxy. The presence of functional groups on the graphene surface leads to chemical interactions between these functional groups on GO and rGO surfaces with the epoxy, contributing to the possible formation of covalent bonds between GO and rGO with the matrix. The presence of oxidation groups on GO also contributes to an improved exfoliation, intercalation, and distribution of the GO sheets in the composites with respect to the rGO based composites.

  11. Chemically specific multiscale modeling of clay-polymer nanocomposites reveals intercalation dynamics, tactoid self-assembly and emergent materials properties.

    Science.gov (United States)

    Suter, James L; Groen, Derek; Coveney, Peter V

    2015-02-01

    A quantitative description is presented of the dynamical process of polymer intercalation into clay tactoids and the ensuing aggregation of polymer-entangled tactoids into larger structures, obtaining various characteristics of these nanocomposites, including clay-layer spacings, out-of-plane clay-sheet bending energies, X-ray diffractograms, and materials properties. This model of clay-polymer interactions is based on a three-level approach, which uses quantum mechanical and atomistic descriptions to derive a coarse-grained yet chemically specific representation that can resolve processes on hitherto inaccessible length and time scales. The approach is applied to study collections of clay mineral tactoids interacting with two synthetic polymers, poly(ethylene glycol) and poly(vinyl alcohol). The controlled behavior of layered materials in a polymer matrix is centrally important for many engineering and manufacturing applications. This approach opens up a route to computing the properties of complex soft materials based on knowledge of their chemical composition, molecular structure, and processing conditions. © 2014 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Earle K. Plyler Prize for Molecular Spectroscopy & Dynamics Lecture: Broadband Rotational Spectroscopy for Chemical Kinetics, Molecular Structure, and Analytical Chemistry

    Science.gov (United States)

    Pate, Brooks

    2013-03-01

    Advances in high-speed digital electronics have enabled a new generation of molecular rotational spectroscopy techniques that provide instantaneous broadband spectral coverage. These techniques use a chirped excitation pulse to coherently excite the molecular sample over a spectral bandwidth of 10 GHz or larger through rapid passage. The subsequent time-domain emission is recorded using high-speed digitizers (up to 100 Gigasample/s) and the frequency domain spectrum is produced by fast Fourier transformation. The chirped-pulse Fourier transform (CP-FT) method has been implemented in the microwave frequency range (2-40 GHz) for studies of cold samples in pulsed jet sources and in the mm-wave/terahertz (THz) frequency range for studies of samples at room-temperature. The method has opened new applications for molecular rotational spectroscopy in the area of chemical kinetics where dynamic rotational spectroscopy is used to measure the rates of unimolecular isomerization reactions in highly excited molecules prepared by pulsed infrared laser excitation. In these applications, the isomerization rate is obtained from an analysis of the overall line shapes which are modified by chemical exchange leading to coalescence behavior similar to the effect in NMR spectroscopy. The sensitivity of the method and the ability to extend it to low frequency (2-8 GHz) have significantly increased the size range of molecules and molecular clusters for structure determination using isotopic substitution to build up the 3D molecular structures atom-by-atom. Application to the structure of water clusters with up to 15 water molecules will be presented. When coupled with advances in solid-state mm-wave/THz devices, this method provides a direct digital technique for analytical chemistry of room-temperature gases based on molecular rotational spectroscopy. These high-throughput methods can analyze complex sample mixtures with unmatched chemical selectivity and short analysis times. Work

  13. Prediction of the Chapman-Jouguet chemical equilibrium state in a detonation wave from first principles based reactive molecular dynamics.

    Science.gov (United States)

    Guo, Dezhou; Zybin, Sergey V; An, Qi; Goddard, William A; Huang, Fenglei

    2016-01-21

    The combustion or detonation of reacting materials at high temperature and pressure can be characterized by the Chapman-Jouguet (CJ) state that describes the chemical equilibrium of the products at the end of the reaction zone of the detonation wave for sustained detonation. This provides the critical properties and product kinetics for input to macroscale continuum simulations of energetic materials. We propose the ReaxFF Reactive Dynamics to CJ point protocol (Rx2CJ) for predicting the CJ state parameters, providing the means to predict the performance of new materials prior to synthesis and characterization, allowing the simulation based design to be done in silico. Our Rx2CJ method is based on atomistic reactive molecular dynamics (RMD) using the QM-derived ReaxFF force field. We validate this method here by predicting the CJ point and detonation products for three typical energetic materials. We find good agreement between the predicted and experimental detonation velocities, indicating that this method can reliably predict the CJ state using modest levels of computation.

  14. Identifying Enclosed Chemical Reaction and Dynamics at the Molecular Level Using Shell-Isolated Miniaturized Plasmonic Liquid Marble.

    Science.gov (United States)

    Han, Xuemei; Lee, Hiang Kwee; Lee, Yih Hong; Hao, Wei; Liu, Yejing; Phang, In Yee; Li, Shuzhou; Ling, Xing Yi

    2016-04-21

    Current microscale tracking of chemical kinetics is limited to destructive ex situ methods. Here we utilize Ag nanocube-based plasmonic liquid marble (PLM) microreactor for in situ molecular-level identification of reaction dynamics. We exploit the ultrasensitive surface-enhanced Raman scattering (SERS) capability imparted by the plasmonic shell to unravel the mechanism and kinetics of aryl-diazonium surface grafting reaction in situ, using just a 2-μL reaction droplet. This reaction is a robust approach to generate covalently functionalized metallic surfaces, yet its kinetics remain unknown to date. Experiments and simulations jointly uncover a two-step sequential grafting process. An initial Langmuir chemisorption of sulfonicbenzene diazonium (dSB) salt onto Ag surfaces forms an intermediate sulfonicbenzene monolayer (Ag-SB), followed by subsequent autocatalytic multilayer growth of Ag-SB3. Kinetic rate constants reveal 19-fold faster chemisorption than multilayer growth. Our ability to precisely decipher molecular-level reaction dynamics creates opportunities to develop more efficient processes in synthetic chemistry and nanotechnology.

  15. Chemical Reactivity Dynamics and Quantum Chaos in Highly Excited Hydrogen Atoms in an External Field: A Quantum Potential Approach

    Directory of Open Access Journals (Sweden)

    B. Maiti

    2002-04-01

    Full Text Available Abstract: Dynamical behavior of chemical reactivity indices like electronegativity, hardness, polarizability, electrophilicity and nucleophilicity indices is studied within a quantum fluid density functional framework for the interactions of a hydrogen atom in its ground electronic state (n = 1 and an excited electronic state (n = 20 with monochromatic and bichromatic laser pulses. Time dependent analogues of various electronic structure principles like the principles of electronegativity equalization, maximum hardness, minimum polarizability and maximum entropy have been found to be operative. Insights into the variation of intensities of the generated higher order harmonics on the color of the external laser field are obtained. The quantum signature of chaos in hydrogen atom has been studied using a quantum theory of motion and quantum fluid dynamics. A hydrogen atom in the electronic ground state (n = 1 and in an excited electronic state ( n = 20 behaves differently when placed in external oscillating monochromatic and bichromatic electric fields. Temporal evolutions of Shannon entropy, quantum Lyapunov exponent and Kolmogorov – Sinai entropy defined in terms of the distance between two initially close Bohmian trajectories for these two cases show marked differences. It appears that a larger uncertainty product and a smaller hardness value signal a chaotic behavior.

  16. Chemical dynamics between wells across a time-dependent barrier: Self-similarity in the Lagrangian descriptor and reactive basins

    Science.gov (United States)

    Junginger, Andrej; Duvenbeck, Lennart; Feldmaier, Matthias; Main, Jörg; Wunner, Günter; Hernandez, Rigoberto

    2017-08-01

    In chemical or physical reaction dynamics, it is essential to distinguish precisely between reactants and products for all times. This task is especially demanding in time-dependent or driven systems because therein the dividing surface (DS) between these states often exhibits a nontrivial time-dependence. The so-called transition state (TS) trajectory has been seen to define a DS which is free of recrossings in a large number of one-dimensional reactions across time-dependent barriers and thus, allows one to determine exact reaction rates. A fundamental challenge to applying this method is the construction of the TS trajectory itself. The minimization of Lagrangian descriptors (LDs) provides a general and powerful scheme to obtain that trajectory even when perturbation theory fails. Both approaches encounter possible breakdowns when the overall potential is bounded, admitting the possibility of returns to the barrier long after the trajectories have reached the product or reactant wells. Such global dynamics cannot be captured by perturbation theory. Meanwhile, in the LD-DS approach, it leads to the emergence of additional local minima which make it difficult to extract the optimal branch associated with the desired TS trajectory. In this work, we illustrate this behavior for a time-dependent double-well potential revealing a self-similar structure of the LD, and we demonstrate how the reflections and side-minima can be addressed by an appropriate modification of the LD associated with the direct rate across the barrier.

  17. 3-D Simulations of the Chemical and Dynamical Evolution of the Galactic Bulge

    CERN Document Server

    Nakasato, N; Nakasato, Naohito; Nomoto, Ken'ichi

    2003-01-01

    A three-dimensional hydrodynamical N-body model for the formation of the Galaxy is presented with special attention to the formation of the bulge component. Starting with cosmologically motivated initial conditions, we obtain a qualitatively similar stellar system to the Galaxy. Then we analyze the chemical and kinematic properties of the bulge stars in our model and find qualitative agreement with observational data. The early evolution of our model has revealed that most bulge stars form during the sub-galactic merger (merger component of the bulge stars). Because of the strong star burst induced by the merger, the metallicity distribution function of such stars becomes as wide as observed. We find that another group of the bulge stars forms later in the inner region of the disk (non-merger component of the bulge stars). Because of the difference in the formation epoch, the main source of iron for this group of stars is different from the merger component. Iron in the merger and non-merger components comes ...

  18. Elucidating collision induced dissociation products and reaction mechanisms of protonated uracil by coupling chemical dynamics simulations with tandem mass spectrometry experiments.

    Science.gov (United States)

    Molina, Estefanía Rossich; Ortiz, Daniel; Salpin, Jean-Yves; Spezia, Riccardo

    2015-12-01

    In this study we have coupled mixed quantum-classical (quantum mechanics/molecular mechanics) direct chemical dynamics simulations with electrospray ionization/tandem mass spectrometry experiments in order to achieve a deeper understanding of the fragmentation mechanisms occurring during the collision induced dissociation of gaseous protonated uracil. Using this approach, we were able to successfully characterize the fragmentation pathways corresponding to ammonia loss (m/z 96), water loss (m/z 95) and cyanic or isocyanic acid loss (m/z 70). Furthermore, we also performed experiments with isotopic labeling completing the fragmentation picture. Remarkably, fragmentation mechanisms obtained from chemical dynamics simulations are consistent with those deduced from isotopic labeling.

  19. Chemical equilibria model of strontium-90 adsorption and transport in soil in response to dynamic alkaline conditions.

    Science.gov (United States)

    Spalding, B P; Spalding, I R

    2001-01-15

    Strontium-90 is a major hazardous contaminant of radioactive wastewater and its processing sludges at many Department of Energy (DOE) facilities. In the past, such contaminated wastewater and sludge have been disposed in soil seepage pits, lagoons, or cribs often under highly perturbed alkaline conditions (pH > 12) where 90Sr solubility is low and its adsorption to surrounding soil is high. As natural weathering returns these soils to near-neutral or slightly acidic conditions, the adsorbed and precipitated calcium and magnesium phases, in which 90Sr is carried, change significantly in both nature and amounts. No comprehensive computational method has been formulated previously to quantitatively simulate the dynamics of 90Sr in the soil-groundwater environment under such dynamic and wide-ranging conditions. A computational code, the Hydrologic Utility Model for Demonstrating Integrated Nuclear Geochemical Environmental Responses (HUMDINGER), was composed to describe the changing equilibria of 90Sr in soil based on its causative chemical reactions including soil buffering, pH-dependent cation-exchange capacity, cation selectivity, and the precipitation/dissolution of calcium carbonate, calcium hydroxide, and magnesium hydroxide in response to leaching groundwater characteristics including pH, acid-neutralizing capacity, dissolved cations, and inorganic carbonate species. The code includes a simulation of one-dimensional transport of 90Sr through a soil column as a series of soil mixing cells where the equilibrium soluble output from one cell is applied to the next cell. Unamended soil leaching and highly alkaline soil treatments, including potassium hydroxide, sodium silicate, and sodium aluminate, were simulated and compared with experimental findings using large (10 kg) soil columns that were leached with 90Sr-contaminated groundwater after treatment. HUMDINGER's simulations were in good agreement with dynamic experimental observations of soil exchange capacity

  20. Chemoproteomics Reveals Chemical Diversity and Dynamics of 4-Oxo-2-nonenal Modifications in Cells.

    Science.gov (United States)

    Sun, Rui; Fu, Ling; Liu, Ke-Ke; Tian, Cai-Ping; Yang, Yong; Tallman, Keri A; Porter, Ned A; Liebler, Daniel C; Yang, Jing

    2017-08-16

    4-Oxo-2-nonenal (ONE) derived from lipid peroxidation modifies nucleophiles and transduces redox signaling by its reactions with proteins. However, the molecular interactions between ONE and complex proteomes and their dynamics in situ remain largely unknown. Here we describe a quantitative chemoproteomic analysis of protein adduction by ONE in cells, in which the cellular target profile of ONE is mimicked by its alkynyl surrogate. The analyses reveal four types of ONE-derived modifications in cells, including ketoamide and Schiff-base adducts to lysine, Michael adducts to cysteine, and a novel pyrrole adducts to cysteine. ONE-derived adducts co-localize and crosstalk with many histone marks and redox sensitive sites. All four types of modifications derived from ONE can be reversed site-specifically in cells. Taken together, our study provides much-needed mechanistic insights into the cellular signaling and potential toxicities associated with this important lipid derived electrophile. Copyright © 2017, The American Society for Biochemistry and Molecular Biology.

  1. [SOUND CONTACTS] Transcendence and immortality in Busoni’s "Doktor Faust"

    Directory of Open Access Journals (Sweden)

    Antonella DiGiulio

    2015-04-01

    Full Text Available The categorization of the many musical and literary works inspired by the Faust legend is based on their two possible conclusions: Faust ends up in hell or is redeemed and attaints heaven. Busoni’s work is often categorized in terms of the redemptive form. I will analyze a third possibility: during the last part of the nineteenth century, philosophers conceptualized that man’s feelings of unhappiness came from his confinement into an eternal recurrence and that life doesn’t end with the death. Scholars tend to ignore the links between Doktor Faust and these philosophical thoughts because of Busoni’s explicit denial of such intentions. And yet Busoni wrote that an opera is the highest form of artistic expression, where music gives words to the unspoken. Therefore I will argue that Busoni characterizes Doktor Faust as a hybridization of the new philosophical theories with literature and music. Busoni’s depiction of the main character in this opera may not be intentional, but the composer summed up all the qualities of Nietzsche’s Übermensch, D’Annunzio’s Superuomo, and Pascoli’s fanciullino in Faust. Faust discovers his own transcendent power, which is independent from the material universe and yet belongs to nature’s laws that are beyond God and the evil. Doktor Faust’s attainment of immortality does not pray for divine redemption and wins out over everything: in this opera, Faust is neither redeemed nor damned. Faust becomes aware that death is nothing but the means that lead to rebirth: “ich, Faust, ein ewiger Wille”.

  2. Quality of life as the concept to resolve/transcend the development paradox

    Directory of Open Access Journals (Sweden)

    Major Đenđi

    2014-01-01

    Full Text Available The central topic of this study is quality of life, which has increasingly gained significance as a topic of social and economic policies in recent years. On the intellectual horizon of public policy, the emphasis has been shifting from the single and ruling aspect of economic growth towards quality of life as a key priority - though the manifestation of this theory in practical measures is badly wanting and rare even in the developed countries. Even in the environments where the shifting of the focus of public policy towards the quality of life is being urged, they are at a loss when trying to define the actual meaning of this term (i.e. quality of life and even more so about the means of measuring it. This study argues that applying the context of quality of life offers a chance to resolve the development paradox. Over emphasizing the importance of economic growth puts an emphasis on the feeling of comfort, which lowers the chance for happiness: psychological research has proven that the source of happiness is returning from a different from-optimal level of activity to the accustomed level. As for the theoretical part, the starting point for the interpretation of the notion of quality of life is the redefinition of the notion of happiness. This redefinition is necessitated by the need to transcend the above-mentioned paradox of modernity. In essence, this paradox is nothing else than the fact that, in the consumer society, ideal consumers are not independent and mature personalities, but mechanical objects that are deprived of their real human relations, are lonely in and of their fears and are exposed to the manipulation of the mass media.

  3. 消费时代的文化超越%The Culture Transcendence in Consumerism Time

    Institute of Scientific and Technical Information of China (English)

    傅永吉

    2011-01-01

    Since the new century, consumerism which generated in developed Western countries has rise in China with globalization and constituted a strong economic and socio-cultural challenges. How to manage the material wealth and achieve the cultural transcendence, in the increasingly affluent physical environment to create balanced, healthy and perfect personality which combined the national tradition cultural advantages with modern democracy sense and self-reliance will, to reverse the decline trend of human life and lead Chinese nation and even all human-being returning to upward pursuit, is the historical and real mission of the cultural renaissance road.%新世纪以来,生成于西方发达国家的消费主义伴随全球化浪潮在中国兴起,构成了强烈的经济和社会文化挑战。如何驾驭物质财富,实现文化超越,在日益富裕的物质生存环境中,造就兼具民族传统人文优势和现代性民主意识及自立自强意志的均衡、健康、完善的人格,逆转人类物化之生命诉求的下降通道,引领中华民族乃至全体人类重归向上寻求生命追求,是文化复兴之路的历史的和现实的命运与使命。

  4. The Dart estuary, Devon, UK: a case study of chemical dynamics and pollutant mobility

    Directory of Open Access Journals (Sweden)

    2007-01-01

    Full Text Available Water, sediments and gill and digestive gland tissues of adult common shore crab (Carcinus maenas, collected at Noss Marina, Sandquay (Britannia Royal Naval College, the Dartmouth Pier, Warfleet Cove and Sugary Cove in the Dart estuary, Devon, UK, were analysed for major, minor and trace elements in spring 2004. Total acid-available measurements analysed included the truly dissolved component and acid-available sediments. Trace metal concentrations are associated largely with particulate and micro-particulate/colloidal phases, the latter being able to pass through standard filter papers. Wide ranges of chemical concentrations were found in the water, sediments and tissues at all the locations. In the water column, 48% of the variance is linked to the sea-salt component (Cl, Na, K, Ca, Mg, B, Li and Sr and the sediment-associated acid-available fractions are linked to Fe-rich lithogenous materials (Ba, Co, Cu, Fe, Mn, V and Zn. In the sediments, trace elements of Cd, Co, Cr, Fe, Pb, Mn, Ni and V are correlated with the sea salts and associated with the fraction of fine sediments within the total sediment. In the gills and the digestive gland tissues of crabs, high concentrations of Al, Cu and Fe are found and there are correlations between acid-available trace metals of Cu, Cr, Fe, Mn, Ni, Sr and Zn. The relationships between trace metal contaminants, their site-specific concentrations, their temporal and spatial variability and the effects of human activities, such as moorland/agriculture with historic mining and recreational activities in the lower Dart estuary, are discussed.

  5. On the chemical dynamics of extracellular polysaccharides in the high Arctic surface microlayer

    Directory of Open Access Journals (Sweden)

    Q. Gao

    2012-01-01

    Full Text Available The surface microlayer (SML represents a unique system of which the physicochemical characteristics may differ from those of the underlying subsurface seawater (SSW. Within the Arctic pack ice area, the SML has been characterized as enriched in small colloids of biological origin, resulting from extracellular polymeric secretions (EPS. During the Arctic Summer Cloud-Ocean Study (ASCOS in August 2008, particulate and dissolved organic matter (POM, DOM samples were collected and chemically characterized from the SML and the corresponding SSW at an open lead centered at 87.5° N and 5° E. Total organic carbon was persistently enriched in the SML with a mean enrichment factor (EF of 1.45 ± 0.41, whereas sporadic depletions of dissolved carbohydrates and amino acids were observed. Monosaccharide compositional analysis reveals that EPS in the Arctic lead was formed mainly of distinctive heteropolysaccharides, enriched in xylose, fucose and glucose. The mean concentrations of total hydrolysable neutral sugars in SSW were 94.9 ± 37.5 nM in high molecular weight (HMW DOM and 64.4 ± 14.5 nM in POM. The enrichment of polysaccharides in the SML appeared to be a common feature, with EFs ranging from 1.7 to 7.0 for particulate polysaccharides and 3.5 to 12.1 for polysaccharides in the HMW DOM fraction. A calculated monosaccharide yield suggests that polymers in the HMW DOM fraction were scavenged, without substantial degradation, into the SML. Bubble scavenging experiments showed that newly aggregated particles could be formed abiotically by coagulation of low molecular weight nanometer-sized gels. Experimentally-generated aerosol particles were enriched in polysaccharides by factors of 22–70, relative to the source seawater. We propose that bubble scavenging of surface-active polysaccharides was one of the possible mechanisms for the enrichment of polysaccharides in the SML.

  6. A stochastic chemical dynamic approach to correlate autoimmunity and optimal vitamin-D range.

    Directory of Open Access Journals (Sweden)

    Susmita Roy

    Full Text Available Motivated by several recent experimental observations that vitamin-D could interact with antigen presenting cells (APCs and T-lymphocyte cells (T-cells to promote and to regulate different stages of immune response, we developed a coarse grained but general kinetic model in an attempt to capture the role of vitamin-D in immunomodulatory responses. Our kinetic model, developed using the ideas of chemical network theory, leads to a system of nine coupled equations that we solve both by direct and by stochastic (Gillespie methods. Both the analyses consistently provide detail information on the dependence of immune response to the variation of critical rate parameters. We find that although vitamin-D plays a negligible role in the initial immune response, it exerts a profound influence in the long term, especially in helping the system to achieve a new, stable steady state. The study explores the role of vitamin-D in preserving an observed bistability in the phase diagram (spanned by system parameters of immune regulation, thus allowing the response to tolerate a wide range of pathogenic stimulation which could help in resisting autoimmune diseases. We also study how vitamin-D affects the time dependent population of dendritic cells that connect between innate and adaptive immune responses. Variations in dose dependent response of anti-inflammatory and pro-inflammatory T-cell populations to vitamin-D correlate well with recent experimental results. Our kinetic model allows for an estimation of the range of optimum level of vitamin-D required for smooth functioning of the immune system and for control of both hyper-regulation and inflammation. Most importantly, the present study reveals that an overdose or toxic level of vitamin-D or any steroid analogue could give rise to too large a tolerant response, leading to an inefficacy in adaptive immune function.

  7. On the chemical dynamics of extracellular polysaccharides in the high Arctic surface microlayer

    Directory of Open Access Journals (Sweden)

    Q. Gao

    2012-07-01

    Full Text Available The surface microlayer (SML represents a unique system of which the physicochemical characteristics may differ from those of the underlying subsurface seawater (SSW. Within the Arctic pack ice area, the SML has been characterized as enriched in small colloids of biological origin, resulting from extracellular polymeric secretions (EPS. During the Arctic Summer Cloud Ocean Study (ASCOS in August 2008, particulate organic matter (POM, with size range > 0.22 μm and dissolved organic matter (DOM, < 0.22 μm, obtained after filtration samples were collected and chemically characterized from the SML and the corresponding SSW at an open lead centered at 87.5° N and 5° E. Total organic carbon was persistently enriched in the SML with a mean enrichment factor (EF of 1.45 ± 0.41, whereas sporadic depletions of dissolved carbohydrates and amino acids were observed. Monosaccharide compositional analysis reveals that EPS in the Arctic lead was formed mainly of distinctive heteropolysaccharides, enriched in xylose, fucose and glucose. The mean concentrations of total hydrolysable neutral sugars in SSW were 94.9 ± 37.5 nM in high molecular weight (HMW DOM (> 5 kDa and 64.4 ± 14.5 nM in POM. The enrichment of polysaccharides in the SML appeared to be a common feature, with EFs ranging from 1.7 to 7.0 for particulate polysaccharides and 3.5 to 12.1 for polysaccharides in the HMW DOM fraction. A calculated monosaccharide yield suggests that polymers in the HMW DOM fraction were scavenged, without substantial degradation, into the SML. Bubble scavenging experiments showed that newly aggregated particles could be formed abiotically by coagulation of low molecular weight nanometer-sized gels. Aerosol particles, artificially generated by bubbling experiments, were enriched in polysaccharides by factors of 22–70, relative to the source seawater. We propose that bubble scavenging of surface-active polysaccharides could be one of the possible mechanisms for the

  8. Microbial population dynamics in an anaerobic CSTR treating a chemical synthesis-based pharmaceutical wastewater.

    Science.gov (United States)

    Oz, Nilgun Ayman; Ince, Orhan; Ince, Bahar Kasapgil; Akarsubasi, Alper Tunga; Eyice, Ozge

    2003-01-01

    Effects of a chemical synthesis based pharmaceutical wastewater on performance of an anaerobic completely stirred tank reactor (CSTR), activity of acetoclastic methanogens and microbial composition were evaluated under various influent compositions. Initially, the CSTR was fed with glucose up to an organic loading rate (OLR) of 6 kg COD/m3 x d corresponding to an F/M ratio of 0.43 with a hydraulic retention time (HRT) of 2.5 days. A COD removal efficiency of 92% and a methane yield of 0.32 m3 CH4/kg COD(removed) were achieved whilst specific methanogenic activity (SMA) was found to be 336mL CH4/gTVS x d. After the CSTR was fed with pre-aerated wastewater diluted by glucose in different dilution ratios of 10% (w/v), 30% (w/v), 70% (w/v), and 100% (w/v) pre-aerated wastewater, gradual decreases in COD removal efficiency to 71%, methane yield to 0.28 m3CH4/kg COD(removed) and SMA to 166 mL CH4/gTVS d occurred whilst volatile fatty acid concentration reached to 1474 mg/L. After the raw wastewater diluted with the pre-aerated wastewater was fed into the CSTR in increasing ratios of 10% (w/v), 30% (w/v), and 60% (w/v), there was a proportional deterioration in performance in terms of COD removal efficiency, methane yield and acetoclastic methanogenic activity. Epifluorescence microscopy of the seed sludge revealed that Methanococcus-like species, short, and medium rods were found to be equally dominant. The short and medium rod species remained equally dominant groups in the CSTR throughout the feeding regime whilst Methanococcus-like species and long rods were found to be in insignificant numbers at the end of the study. Changes in archael diversity were determined using molecular analyses such as polymerase chain reaction (PCR), and denaturent gradient gel electrophoresis (DGGE). Results showed that overall archeal diversity did not change much whereas changes in composition of eubacterial population occurred.

  9. Plant-symbiotic fungi as chemical engineers: multi-genome analysis of the clavicipitaceae reveals dynamics of alkaloid loci.

    Directory of Open Access Journals (Sweden)

    Christopher L Schardl

    Full Text Available The fungal family Clavicipitaceae includes plant symbionts and parasites that produce several psychoactive and bioprotective alkaloids. The family includes grass symbionts in the epichloae clade (Epichloë and Neotyphodium species, which are extraordinarily diverse both in their host interactions and in their alkaloid profiles. Epichloae produce alkaloids of four distinct classes, all of which deter insects, and some-including the infamous ergot alkaloids-have potent effects on mammals. The exceptional chemotypic diversity of the epichloae may relate to their broad range of host interactions, whereby some are pathogenic and contagious, others are mutualistic and vertically transmitted (seed-borne, and still others vary in pathogenic or mutualistic behavior. We profiled the alkaloids and sequenced the genomes of 10 epichloae, three ergot fungi (Claviceps species, a morning-glory symbiont (Periglandula ipomoeae, and a bamboo pathogen (Aciculosporium take, and compared the gene clusters for four classes of alkaloids. Results indicated a strong tendency for alkaloid loci to have conserved cores that specify the skeleton structures and peripheral genes that determine chemical variations that are known to affect their pharmacological specificities. Generally, gene locations in cluster peripheries positioned them near to transposon-derived, AT-rich repeat blocks, which were probably involved in gene losses, duplications, and neofunctionalizations. The alkaloid loci in the epichloae had unusual structures riddled with large, complex, and dynamic repeat blocks. This feature was not reflective of overall differences in repeat contents in the genomes, nor was it characteristic of most other specialized metabolism loci. The organization and dynamics of alkaloid loci and abundant repeat blocks in the epichloae suggested that these fungi are under selection for alkaloid diversification. We suggest that such selection is related to the variable life histories

  10. Plant-symbiotic fungi as chemical engineers: multi-genome analysis of the clavicipitaceae reveals dynamics of alkaloid loci.

    Science.gov (United States)

    Schardl, Christopher L; Young, Carolyn A; Hesse, Uljana; Amyotte, Stefan G; Andreeva, Kalina; Calie, Patrick J; Fleetwood, Damien J; Haws, David C; Moore, Neil; Oeser, Birgitt; Panaccione, Daniel G; Schweri, Kathryn K; Voisey, Christine R; Farman, Mark L; Jaromczyk, Jerzy W; Roe, Bruce A; O'Sullivan, Donal M; Scott, Barry; Tudzynski, Paul; An, Zhiqiang; Arnaoudova, Elissaveta G; Bullock, Charles T; Charlton, Nikki D; Chen, Li; Cox, Murray; Dinkins, Randy D; Florea, Simona; Glenn, Anthony E; Gordon, Anna; Güldener, Ulrich; Harris, Daniel R; Hollin, Walter; Jaromczyk, Jolanta; Johnson, Richard D; Khan, Anar K; Leistner, Eckhard; Leuchtmann, Adrian; Li, Chunjie; Liu, JinGe; Liu, Jinze; Liu, Miao; Mace, Wade; Machado, Caroline; Nagabhyru, Padmaja; Pan, Juan; Schmid, Jan; Sugawara, Koya; Steiner, Ulrike; Takach, Johanna E; Tanaka, Eiji; Webb, Jennifer S; Wilson, Ella V; Wiseman, Jennifer L; Yoshida, Ruriko; Zeng, Zheng

    2013-01-01

    The fungal family Clavicipitaceae includes plant symbionts and parasites that produce several psychoactive and bioprotective alkaloids. The family includes grass symbionts in the epichloae clade (Epichloë and Neotyphodium species), which are extraordinarily diverse both in their host interactions and in their alkaloid profiles. Epichloae produce alkaloids of four distinct classes, all of which deter insects, and some-including the infamous ergot alkaloids-have potent effects on mammals. The exceptional chemotypic diversity of the epichloae may relate to their broad range of host interactions, whereby some are pathogenic and contagious, others are mutualistic and vertically transmitted (seed-borne), and still others vary in pathogenic or mutualistic behavior. We profiled the alkaloids and sequenced the genomes of 10 epichloae, three ergot fungi (Claviceps species), a morning-glory symbiont (Periglandula ipomoeae), and a bamboo pathogen (Aciculosporium take), and compared the gene clusters for four classes of alkaloids. Results indicated a strong tendency for alkaloid loci to have conserved cores that specify the skeleton structures and peripheral genes that determine chemical variations that are known to affect their pharmacological specificities. Generally, gene locations in cluster peripheries positioned them near to transposon-derived, AT-rich repeat blocks, which were probably involved in gene losses, duplications, and neofunctionalizations. The alkaloid loci in the epichloae had unusual structures riddled with large, complex, and dynamic repeat blocks. This feature was not reflective of overall differences in repeat contents in the genomes, nor was it characteristic of most other specialized metabolism loci. The organization and dynamics of alkaloid loci and abundant repeat blocks in the epichloae suggested that these fungi are under selection for alkaloid diversification. We suggest that such selection is related to the variable life histories of the

  11. Application of computational fluid dynamics to regional dosimetry of inhaled chemicals in the upper respiratory tract of the rat.

    Science.gov (United States)

    Kimbell, J S; Gross, E A; Joyner, D R; Godo, M N; Morgan, K T

    1993-08-01

    For certain inhaled air pollutants, such as reactive, water soluble gases, the distribution of nasal lesions observed in F344 rats may be closely related to regional gas uptake patterns in the nose. These uptake patterns can be influenced by the currents of air flowing through the upper respiratory tract during the breathing cycle. Since data on respiratory tract lesions in F344 rats are extrapolated to humans to make predictions of risk to human health, a better understanding of the factors affecting these responses is needed. To assess potential effects of nasal airflow on lesion location and severity, a methodology was developed for creation of computer simulations of steady-state airflow and gas transport using a three-dimensional finite element grid reconstructed from serial step-sections of the nasal passages of a male F344 rat. Simulations on a supercomputer used the computational fluid dynamics package FIDAP (FDI, Evanston, IL). Distinct streams of bulk flow evident in the simulations matched inspiratory streams reported for the F344 rat. Moreover, simulated regional flow velocities matched measured velocities in concurrent laboratory experiments with a hollow nasal mold. Computer-predicted flows were used in simulations of gas transport to nasal passage walls, with formaldehyde as a test case. Results from the uptake simulations were compared with the reported distribution of formaldehyde-induced nasal lesions observed in the F344 rat, and indicated that airflow-driven uptake patterns probably play an important role in determining the location of certain nasal lesions induced by formaldehyde. This work demonstrated the feasibility of applying computational fluid dynamics to airflow-driven dosimetry of inhaled chemicals in the upper respiratory tract.

  12. Chemical Reaction Rates from Ring Polymer Molecular Dynamics: Zero Point Energy Conservation in Mu + H2 → MuH + H.

    Science.gov (United States)

    Pérez de Tudela, Ricardo; Aoiz, F J; Suleimanov, Yury V; Manolopoulos, David E

    2012-02-16

    A fundamental issue in the field of reaction dynamics is the inclusion of the quantum mechanical (QM) effects such as zero point energy (ZPE) and tunneling in molecular dynamics simulations, and in particular in the calculation of chemical reaction rates. In this work we study the chemical reaction between a muonium atom and a hydrogen molecule. The recently developed ring polymer molecular dynamics (RPMD) technique is used, and the results are compared with those of other methods. For this reaction, the thermal rate coefficients calculated with RPMD are found to be in excellent agreement with the results of an accurate QM calculation. The very minor discrepancies are within the convergence error even at very low temperatures. This exceptionally good agreement can be attributed to the dominant role of ZPE in the reaction, which is accounted for extremely well by RPMD. Tunneling only plays a minor role in the reaction.

  13. On the Paradox of the Political/Transcendence and Eschatology: Transimmanence and the Promise of Love in Jean-Luc Nancy

    Directory of Open Access Journals (Sweden)

    Schalk Hendrik Gerber

    2017-02-01

    Full Text Available The debate on the possibility of re-thinking transcendence at the so-called end or closure of the metaphysical tradition and its relation to the political is situated at the heart of contemporary continental philosophy of religion. This article engages the debate by reviewing what is to be thought or anticipated at the closure. Firstly, the problem of engaging with transcendence at the closure of metaphysics is outlined as a discussion on what is possibly meant by the end of transcendence and onto-theology. Subsequently, the question concerning the political and its inseparable relation to transcendence is sketched and denoted by the phrase “the political/transcendence”. Secondly, Levinas’ and Nancy’s respective attempts at addressing the problem are explored in the form of a debate, with the outcome suggesting a possible gesture towards Nancy’s reconception of transcendence as transimmanence, found in his notion of “the promise of love”, on “how” to anticipate rather than “what” to anticipate in these end times.

  14. Chemical dynamics of acidity and heavy metals in a mine water-polluted soil during decontamination using clean water.

    Science.gov (United States)

    Chen, A; Lin, C; Lu, W; Ma, Y; Bai, Y; Chen, H; Li, J

    2010-03-15

    A column leaching experiment was conducted to investigate the chemical dynamics of the percolating water and washed soil during decontamination of an acidic mine water-polluted soil. The results show that leaching of the contaminated soil with clean water rapidly reduced soluble acidity and ion concentrations in the soils. However, only water over a long period of time. During the column leaching, dissolved Cu and Pb were rapidly leached out, followed by mobilization of colloidal Cu and Pb from the exchangeable and the oxide-bound fractions as a result of reduced ionic strength in the soil solution. The soluble Fe contained in the soil was rare, probably because the soil pH was not sufficiently low; marked mobility of colloidal Fe took place after the ionic strength of the percolating water was weakened and the mobilized Fe was mainly derived from iron oxides. In contrast with Cu, Pb and Fe, the concentration of leachate Zn and Mn showed a continuously decreasing trend during the entire period of the experiment.

  15. A Molecular Dynamics Investigation of the Physical-Chemical Properties of Calicivirus Capsid Protein Adsorption to Fomites

    Science.gov (United States)

    Peeler, David; Matysiak, Silvina

    2013-03-01

    Any inanimate object with an exposed surface bears the possibility of hosting a virus and may therefore be labeled a fomite. This research hopes to distinguish which chemical-physical differences in fomite surface and virus capsid protein characteristics cause variations in virus adsorption through an alignment of in silico molecular dynamics simulations with in vitro measurements. The impact of surface chemistry on the adsorption of the human norovirus (HNV)-surrogate calicivirus capsid protein 2MS2 has been simulated for monomer and trimer structures and is reported in terms of protein-self assembled monolayer (SAM) binding free energy. The coarse-grained MARTINI forcefield was used to maximize spatial and temporal resolution while minimizing computational load. Future work will investigate the FCVF5 and SMSVS4 calicivirus trimers and will extend beyond hydrophobic and hydrophilic SAM surface chemistry to charged SAM surfaces in varying ionic concentrations. These results will be confirmed by quartz crystal microbalance experiments conducted by Dr. Wigginton at the University of Michigan. This should provide a novel method for predicting the transferability of viruses that cannot be studied in vitro such as dangerous foodborne and nosocomially-acquired viruses like HNV.

  16. Dynamic stiffness of chemically and physically ageing rubber vibration isolators in the audible frequency range: Part 2—waveguide solution

    Science.gov (United States)

    Kari, Leif

    2017-09-01

    The dynamic stiffness of a chemically and physically ageing rubber vibration isolator in the audible frequency range is modelled as a function of ageing temperature, ageing time, actual temperature, time, frequency and isolator dimension. In particular, the dynamic stiffness for an axially symmetric, homogeneously aged rubber vibration isolator is derived by waveguides where the eigenmodes given by the dispersion relation for an infinite cylinder satisfying traction free radial surface boundary condition are matched to satisfy the displacement boundary conditions at the lateral surface ends of the finite rubber cylinder. The constitutive equations are derived in a companion paper (Part 1). The dynamic stiffness is calculated over the whole audible frequency range 20-20,000 Hz at several physical ageing times for a temperature history starting at thermodynamic equilibrium at +25°C and exposed by a sudden temperature step down to -60°C and at several chemical ageing times at temperature +25°C with simultaneous molecular network scission and reformation. The dynamic stiffness results are displaying a strong frequency dependence at a short physical ageing time, showing stiffness magnitude peaks and troughs, and a strong physical ageing time dependence, showing a large stiffness magnitude increase with the increased physical ageing time, while the peaks and troughs are smoothed out. Likewise, stiffness magnitude peaks and troughs are frequency-shifted with increased chemical ageing time. The developed model is possible to apply for dynamic stiffness prediction of rubber vibration isolator over a broad audible frequency range under realistic environmental condition of chemical ageing, mainly attributed to oxygen exposure from outside and of physical ageing, primarily perceived at low-temperature steps.

  17. Identification and Quantification of Volatile Chemical Spoilage Indexes Associated with Bacterial Growth Dynamics in Aerobically Stored Chicken.

    Science.gov (United States)

    Mikš-Krajnik, Marta; Yoon, Yong-Jin; Ukuku, Dike O; Yuk, Hyun-Gyun

    2016-08-01

    Volatile organic compounds (VOCs) as chemical spoilage indexes (CSIs) of raw chicken breast stored aerobically at 4, 10, and 21 °C were identified and quantified using solid phase microextraction (SPME) combined with gas chromatography-mass spectrometry (GC-MS). The growth dynamics of total viable count (TVC), psychrotrophs, Pseudomonas spp., lactic acid bacteria (LAB), Brochothrix thermosphacta and H2 S producing bacteria were characterized based on maximum growth rates (μmax ), maximal microbial concentration (Nmax ) and at the moment of microbial shelf life (Svalues ), calculated from Gompertz-fitted growth curves. Pseudomonas spp. was predominant species, while B. thermosphacta was characterized by the highest μmax . The microbiological and sensory shelf lives were estimated based on TVC, Pseudomonas spp., and B. thermosphacta counts and sensory evaluation, respectively. Among 27 VOCs identified by GC-MS in spoiled chicken samples, ethanol (EtOH), 1-butanol-3-methyl (1But-3M), and acetic acid (C2 ) achieved the highest Pearson's correlation coefficients of 0.66, 0.61, and 0.59, respectively, with TVC, regardless of storage temperature. Partial least squares (PLS) regression revealed that the synthesis of 1But-3M and C2 was most likely induced by the metabolic activity of B. thermosphacta and LAB, while EtOH was attributed to Pseudomonas spp. The increase in concentration of selected volatile spoilage markers (EtOH, 1But-3M, and C2 ) in the headspace over spoiled chicken breast was found to be statistically significant (P < 0.05) with TVC growth. These findings highlight the possibility of analyzing the combination of 3 selected spoilage markers: EtOH, 1But-3M, and C2 as rapid evaluation for poultry quality testing using SPME-GC-MS.

  18. The reactivation of tabun-inhibited mutant AChE with Ortho-7: steered molecular dynamics and quantum chemical studies.

    Science.gov (United States)

    Lo, Rabindranath; Chandar, Nellore Bhanu; Ghosh, Shibaji; Ganguly, Bishwajit

    2016-04-01

    A highly toxic nerve agent, tabun, can inhibit acetylcholinesterase (AChE) at cholinergic sites, which leads to serious cardiovascular complications, respiratory compromise and death. We have examined the structural features of the tabun-conjugated AChE complex with an oxime reactivator, Ortho-7, to provide a strategy for designing new and efficient reactivators. Mutation of mAChE within the choline binding site by Y337A and F338A and its interaction with Ortho-7 has been investigated using steered molecular dynamics (SMD) and quantum chemical methods. The overall study shows that after mutagenesis (Y337A), the reactivator can approach more freely towards the phosphorylated active site of serine without any significant steric hindrance in the presence of tabun compared to the wild type and double mutant. Furthermore, the poor binding of Ortho-7 with the peripheral residues of mAChE in the case of the single mutant compared to that of the wild-type and double mutant (Y337A/F338A) can contribute to better efficacy in the former case. Ortho-7 has formed a greater number of hydrogen bonds with the active site surrounding residues His447 and Phe295 in the case of the single mutant (Y337A), and that stabilizes the drug molecule for an effective reactivation process. The DFT M05-2X/6-31+G(d) level of theory shows that the binding energy of Ortho-7 with the single mutant (Y337A) is energetically more preferred (-19.8 kcal mol(-1)) than the wild-type (-8.1 kcal mol(-1)) and double mutant (Y337A/F338A) (-16.0 kcal mol(-1)). The study reveals that both the orientation of the oxime reactivator for nucleophilic attack and the stabilization of the reactivator at the active site would be crucial for the design of an efficient reactivator.

  19. Dynamics of 3D representation of interfaces in UV-induced chemical vapor deposition: experiments, modeling, and simulation for silicon nitride thin layers

    Science.gov (United States)

    Flicstein, Jean; Guillonneau, E.; Marquez, Jose; How Kee Chun, L. S.; Maisonneuve, D.; David, C.; Wang, Zh. Z.; Palmier, Jean F.; Courant, J. L.

    2001-06-01

    We study the surface dynamics of silicon nitride films deposited by UV-induced low pressure chemical vapor pressure. Atomic force microscopy measurements show that the surface reaches a scale invariant stationary state coherent wit the Kardar-Parisi-Zhang (KPZ) equation. Discrete geometry techniques are oriented to extra morphological characteristics of surface and bulk which corresponds to computer simulated photodeposit. This allows to determine the physical origin of KPZ scaling to be al ow value of the surface sticking probability, and connected to the surface concentration of activate charged centers, which permits to start the evaluation of the Monte Carlo-molecular dynamics simulator.

  20. Progress in spin dynamics solid-state nuclear magnetic resonance with the application of Floquet-Magnus expansion to chemical shift anisotropy.

    Science.gov (United States)

    Mananga, Eugene Stephane

    2013-01-01

    The purpose of this article is to present an historical overview of theoretical approaches used for describing spin dynamics under static or rotating experiments in solid state nuclear magnetic resonance. The article gives a brief historical overview for major theories in nuclear magnetic resonance and the promising theories. We present the first application of Floquet-Magnus expansion to chemical shift anisotropy when irradiated by BABA pulse sequence.

  1. Reaction dynamics. Extremely short-lived reaction resonances in Cl + HD (v = 1) → DCl + H due to chemical bond softening.

    Science.gov (United States)

    Yang, Tiangang; Chen, Jun; Huang, Long; Wang, Tao; Xiao, Chunlei; Sun, Zhigang; Dai, Dongxu; Yang, Xueming; Zhang, Dong H

    2015-01-02

    The Cl + H2 reaction is an important benchmark system in the study of chemical reaction dynamics that has always appeared to proceed via a direct abstraction mechanism, with no clear signature of reaction resonances. Here we report a high-resolution crossed-molecular beam study on the Cl + HD (v = 1, j = 0) → DCl + H reaction (where v is the vibrational quantum number and j is the rotational quantum number). Very few forward scattered products were observed. However, two distinctive peaks at collision energies of 2.4 and 4.3 kilocalories per mole for the DCl (v' = 1) product were detected in the backward scattering direction. Detailed quantum dynamics calculations on a highly accurate potential energy surface suggested that these features originate from two very short-lived dynamical resonances trapped in the peculiar H-DCl (v' = 2) vibrational adiabatic potential wells that result from chemical bond softening. We anticipate that dynamical resonances trapped in such wells exist in many reactions involving vibrationally excited molecules.

  2. Effect of sucrose on chemically and thermally induced unfolding of domain-I of human serum albumin: Solvation dynamics and fluorescence anisotropy study.

    Science.gov (United States)

    Yadav, Rajeev; Sengupta, Bhaswati; Sen, Pratik

    2016-04-01

    The present study is devoted to understand the effect of sucrose on the hydration dynamics and rotational relaxation dynamics within the domain-I of HSA during chemically as well as thermally induced unfolding. It has been observed that the average solvation time become slower in the presence of sucrose for the lower concentrations of GnHCl, however at higher concentrations of GnHCl the effect of sucrose is almost negligible. From the time resolved fluorescence anisotropy it has been observed that in the lower concentration region of GnHCl the sucrose induced stabilization is small as compared to the higher concentrations of GnHCl. We have concluded that the hydration dynamics plays an important role in the sucrose induced stabilization process at the low concentration region; whereas environmental restriction is responsible at the higher concentration of GnHCl. However, we have observed a negligible stabilizing effect of sucrose towards the temperature induced unfolding.

  3. The Philosophical Sinification of Modernity and the Modern Confucian Paradigm of Immanent Transcendence (內在超越性

    Directory of Open Access Journals (Sweden)

    Jana S. ROŠKER

    2014-05-01

    Full Text Available As a major source of social values, Modern Confucian theory assumes essential significance amidst the proliferation of instrumental rationality in contemporary China. This current is distinguished by a multifaceted attempt to revitalize traditional thought by means of new influences borrowed or derived from Western systems. It defines itself with a search for a synthesis between “Western” and traditional Chinese thought, aiming to elaborate a new system of ideas and values, suitable for the modern, globalized society. The present contribution examines the ways in which 3rd generation of Modern Confucian philosophers changed the framework within which traditional Chinese philosophical inquiry has been carried out, exposing the importance of immanent transcendence.

  4. Hot spot formation and chemical reaction initiation in shocked HMX crystals with nanovoids: a large-scale reactive molecular dynamics study.

    Science.gov (United States)

    Zhou, Tingting; Lou, Jianfeng; Zhang, Yangeng; Song, Huajie; Huang, Fenglei

    2016-07-14

    We report million-atom reactive molecular dynamic simulations of shock initiation of β-cyclotetramethylene tetranitramine (β-HMX) single crystals containing nanometer-scale spherical voids. Shock induced void collapse and subsequent hot spot formation as well as chemical reaction initiation are observed which depend on the void size and impact strength. For an impact velocity of 1 km s(-1) and a void radius of 4 nm, the void collapse process includes three stages; the dominant mechanism is the convergence of upstream molecules toward the centerline and the downstream surface of the void forming flowing molecules. Hot spot formation also undergoes three stages, and the principal mechanism is kinetic energy transforming to thermal energy due to the collision of flowing molecules on the downstream surface. The high temperature of the hot spot initiates a local chemical reaction, and the breakage of the N-NO2 bond plays the key role in the initial reaction mechanism. The impact strength and void size have noticeable effects on the shock dynamical process, resulting in a variation of the predominant mechanisms leading to void collapse and hot spot formation. Larger voids or stronger shocks result in more intense hot spots and, thus, more violent chemical reactions, promoting more reaction channels and generating more reaction products in a shorter duration. The reaction products are mainly concentrated in the developed hot spot, indicating that the chemical reactivity of the hmx crystal is greatly enhanced by void collapse. The detailed information derived from this study can aid a thorough understanding of the role of void collapse in hot spot formation and the chemical reaction initiation of explosives.

  5. Using the Seismology of Non-magnetic Chemically Peculiar Stars as a Probe of Dynamical Processes in Stellar Interiors

    Indian Academy of Sciences (India)

    Sylvain Turcotte

    2005-06-01

    Chemical composition is a good tracer of the hydrodynamical processes that occur in stars as they often lead to mixing and particle transport. By comparing abundances predicted by models and those observed in stars we can infer some constraints on those mixing processes. As pulsations in the stars are often very sensitive to chemical composition, we can use asteroseismology to probe the internal chemical composition of stars where no direct observations are possible. In this paper I focus on main sequence stars Am, Bootis, and HgMn stars and discuss what we can learn of mixing processes in these stars from seismology.

  6. Using the seismology of non-magnetic chemically peculiar stars as a probe of dynamical processes in stellar interiors

    CERN Document Server

    Turcotte, S

    2005-01-01

    Chemical composition is a good tracer of hydrodynamical processes that occur in stars as they often lead to mixing and particle transport. By comparing abundances predicted by models and those observed in stars we can infer some constraints on those mixing processes. As pulsations in stars are often very sensitive to chemical composition, we can use asteroseismology to probe the internal chemical composition of stars where no direct observations are possible. In this paper I focus on main sequence stars Am, lambda bootis, and HgMn stars and discuss what we can learn of mixing processes in those stars from seismology.

  7. 129Xe NMR chemical shift in Xe@C60 calculated at experimental conditions: essential role of the relativity, dynamics, and explicit solvent.

    Science.gov (United States)

    Standara, Stanislav; Kulhánek, Petr; Marek, Radek; Straka, Michal

    2013-08-15

    The isotropic (129)Xe nuclear magnetic resonance (NMR) chemical shift (CS) in Xe@C60 dissolved in liquid benzene was calculated by piecewise approximation to faithfully simulate the experimental conditions and to evaluate the role of different physical factors influencing the (129)Xe NMR CS. The (129)Xe shielding constant was obtained by averaging the (129)Xe nuclear magnetic shieldings calculated for snapshots obtained from the molecular dynamics trajectory of the Xe@C60 system embedded in a periodic box of benzene molecules. Relativistic corrections were added at the Breit-Pauli perturbation theory (BPPT) level, included the solvent, and were dynamically averaged. It is demonstrated that the contribution of internal dynamics of the Xe@C60 system represents about 8% of the total nonrelativistic NMR CS, whereas the effects of dynamical solvent add another 8%. The dynamically averaged relativistic effects contribute by 9% to the total calculated (129)Xe NMR CS. The final theoretical value of 172.7 ppm corresponds well to the experimental (129)Xe CS of 179.2 ppm and lies within the estimated errors of the model. The presented computational protocol serves as a prototype for calculations of (129)Xe NMR parameters in different Xe atom guest-host systems. Copyright © 2013 Wiley Periodicals, Inc.

  8. Soil pH Dynamics and Nitrogen Transformations Under Long-Term Chemical Fertilization in Four Typical Chinese Croplands

    Institute of Scientific and Technical Information of China (English)

    MENG Hong-qi; XU Ming-gang; L Jia-long; HE Xin-hua; LI Jian-wei; SHI Xiao-jun; PENG Chang; WANG Bo-ren; ZHANG Hui-min

    2013-01-01

    Long-term fertilization experiment provides the platform for understanding the proton budgets in nitrogen transformations of agricultural ecosystems. We analyzed the historical (1990-2005) observations on four agricultural long-term experiments in China (Changping, Chongqing, Gongzhuling and Qiyang) under four different fertilizations, i.e., no-fertilizer (control), sole chemical nitrogen fertilizer (FN), sole chemical phosphorous and potassium fertilizers (FPK) and chemical nitrogen, phosphorous and potassium fertilizers (FNPK). The significant decline in topsoil pH was caused not only by chemical N fertilization (0.29 and 0.89∆pH at Gongzhuling and Qiyang, respectively) but also by chemical PK fertilization (0.59∆pH at Gongzhuling). The enhancement of available nutrients in the topsoil due to long-term direct nutrients supply with chemical fertilizers was in the descending order of available P (168-599%)>available K (16-189%)>available N (9-33%). The relative rate of soil pH decline was lower under long-term judicious chemical fertilization (-0.036-0.034 ∆pH yr-1) than that under long-term sole N or PK fertilization (0.016-0.086 ∆pH yr-1). Long-term judicious chemical fertilization with N, P and K elements decreases the nutritional limitation to normal crop growth, under which more N output was distributed in biomass removal rather than the loss via nitrate leaching. We concluded that the N distribution percentage of nitrate leaching to biomass removal might be a suitable indicator to the sensitivity of agricultural ecosystems to acid inputs.

  9. Dynamic modeling of chemical fate and transport in multimedia environments at watershed scale-I: theoretical considerations and model implementation.

    Science.gov (United States)

    Luo, Yuzhou; Gao, Qiong; Yang, Xiusheng

    2007-04-01

    A geo-referenced environmental fate model was developed for analyzing unsteady-state dispersion and distribution of chemicals in multimedia environmental systems. Chemical transport processes were formulated in seven environmental compartments of air, canopy, surface soil, root-zone soil, vadose-zone soil, surface water, and sediment. The model assumed that the compartments were completely mixed and chemical equilibrium was established instantaneously between the sub-compartments within each compartment. A fugacity approach was utilized to formulate the mechanisms of diffusion, advection, physical interfacial transport, and transformation reactions. The governing equations of chemical mass balances in the environmental compartments were solved simultaneously to reflect the interactions between the compartments. A geographic information system (GIS) database and geospatial analysis were integrated into the chemical transport simulation to provide spatially explicit estimations of model parameters at watershed scale. Temporal variations of the environmental properties and source emissions were also considered in the parameter estimations. The outputs of the model included time-dependent chemical concentrations in each compartment and its sub-compartments, and inter-media mass fluxes between adjacent compartments at daily time steps.

  10. Toward structural dynamics: protein motions viewed by chemical shift modulations and direct detection of C'N multiple-quantum relaxation.

    Science.gov (United States)

    Mori, Mirko; Kateb, Fatiha; Bodenhausen, Geoffrey; Piccioli, Mario; Abergel, Daniel

    2010-03-17

    Multiple quantum relaxation in proteins reveals unexpected relationships between correlated or anti-correlated conformational backbone dynamics in alpha-helices or beta-sheets. The contributions of conformational exchange to the relaxation rates of C'N coherences (i.e., double- and zero-quantum coherences involving backbone carbonyl (13)C' and neighboring amide (15)N nuclei) depend on the kinetics of slow exchange processes, as well as on the populations of the conformations and chemical shift differences of (13)C' and (15)N nuclei. The relaxation rates of C'N coherences, which reflect concerted fluctuations due to slow chemical shift modulations (CSMs), were determined by direct (13)C detection in diamagnetic and paramagnetic proteins. In well-folded proteins such as lanthanide-substituted calbindin (CaLnCb), copper,zinc superoxide dismutase (Cu,Zn SOD), and matrix metalloproteinase (MMP12), slow conformational exchange occurs along the entire backbone. Our observations demonstrate that relaxation rates of C'N coherences arising from slow backbone dynamics have positive signs (characteristic of correlated fluctuations) in beta-sheets and negative signs (characteristic of anti-correlated fluctuations) in alpha-helices. This extends the prospects of structure-dynamics relationships to slow time scales that are relevant for protein function and enzymatic activity.

  11. Laboratory of Chemical Physics

    Data.gov (United States)

    Federal Laboratory Consortium — Current research in the Laboratory of Chemical Physics is primarily concerned with experimental, theoretical, and computational problems in the structure, dynamics,...

  12. Chemically Induced Dynamic Nuclear Polarization during the Thermolysis of Alkoxyamines: A New Approach to Detect the Occurrence of H-Transfer Reactions

    Directory of Open Access Journals (Sweden)

    Elena Bagryanskaya

    2010-09-01

    Full Text Available Thermal decomposition of alkoxyamines in the presence of scavengers was found to proceed with the formation of chemically induced nuclear polarization detected by 1H NMR. The distinctive Chemically Induced Dynamic Nuclear Polarization (CIDNP features were studied using the example of three alkoxyamines: 4-nitrophenyl 2-(2,2,6,6-tetramethylpiperidin-1-yloxy-2-methylpropanoate (1a, 4-nitrophenyl 2-(2,2-diphenyl-3-phenylimino-2,3-dihydroindol-1-yloxy-2-methylpropanoate (2a and 4-nitrophenyl 2-(2,2,5,5-tetramethyl-4-phenyl-2H-imidazol-1-oxy-2-methylpropanoate (3a in the presence of PhSH. The analysis of CIDNP signs of methacrylate protons allows us to conclude on the occurrence of hydrogen atom transfer reaction in geminate radical pair formed in alkoxyamine thermolysis. Thus, CIDNP is a fast and sensitive method to detect the occurrence of intra/intermolecular hydrogen transfer in alkoxyamine thermolysis.

  13. Dynamics

    CERN Document Server

    Goodman, Lawrence E

    2001-01-01

    Beginning text presents complete theoretical treatment of mechanical model systems and deals with technological applications. Topics include introduction to calculus of vectors, particle motion, dynamics of particle systems and plane rigid bodies, technical applications in plane motions, theory of mechanical vibrations, and more. Exercises and answers appear in each chapter.

  14. Predicting Fecundity of Fathead Minnows (Pimephales promelas Exposed to Endocrine-Disrupting Chemicals Using a MATLAB®-Based Model of Oocyte Growth Dynamics.

    Directory of Open Access Journals (Sweden)

    Karen H Watanabe

    Full Text Available Fish spawning is often used as an integrated measure of reproductive toxicity, and an indicator of aquatic ecosystem health in the context of forecasting potential population-level effects considered important for ecological risk assessment. Consequently, there is a need for flexible, widely-applicable, biologically-based models that can predict changes in fecundity in response to chemical exposures, based on readily measured biochemical endpoints, such as plasma vitellogenin (VTG concentrations, as input parameters. Herein we describe a MATLAB® version of an oocyte growth dynamics model for fathead minnows (Pimephales promelas with a graphical user interface based upon a previously published model developed with MCSim software and evaluated with data from fathead minnows exposed to an androgenic chemical, 17β-trenbolone. We extended the evaluation of our new model to include six chemicals that inhibit enzymes involved in steroid biosynthesis: fadrozole, ketoconazole, propiconazole, prochloraz, fenarimol, and trilostane. In addition, for unexposed fathead minnows from group spawning design studies, and those exposed to the six chemicals, we evaluated whether the model is capable of predicting the average number of eggs per spawn and the average number of spawns per female, which was not evaluated previously. The new model is significantly improved in terms of ease of use, platform independence, and utility for providing output in a format that can be used as input into a population dynamics model. Model-predicted minimum and maximum cumulative fecundity over time encompassed the observed data for fadrozole and most propiconazole, prochloraz, fenarimol and trilostane treatments, but did not consistently replicate results from ketoconazole treatments. For average fecundity (eggs•female(-1•day(-1, eggs per spawn, and the number of spawns per female, the range of model-predicted values generally encompassed the experimentally observed values

  15. Predicting Fecundity of Fathead Minnows (Pimephales promelas) Exposed to Endocrine-Disrupting Chemicals Using a MATLAB®-Based Model of Oocyte Growth Dynamics.

    Science.gov (United States)

    Watanabe, Karen H; Mayo, Michael; Jensen, Kathleen M; Villeneuve, Daniel L; Ankley, Gerald T; Perkins, Edward J

    2016-01-01

    Fish spawning is often used as an integrated measure of reproductive toxicity, and an indicator of aquatic ecosystem health in the context of forecasting potential population-level effects considered important for ecological risk assessment. Consequently, there is a need for flexible, widely-applicable, biologically-based models that can predict changes in fecundity in response to chemical exposures, based on readily measured biochemical endpoints, such as plasma vitellogenin (VTG) concentrations, as input parameters. Herein we describe a MATLAB® version of an oocyte growth dynamics model for fathead minnows (Pimephales promelas) with a graphical user interface based upon a previously published model developed with MCSim software and evaluated with data from fathead minnows exposed to an androgenic chemical, 17β-trenbolone. We extended the evaluation of our new model to include six chemicals that inhibit enzymes involved in steroid biosynthesis: fadrozole, ketoconazole, propiconazole, prochloraz, fenarimol, and trilostane. In addition, for unexposed fathead minnows from group spawning design studies, and those exposed to the six chemicals, we evaluated whether the model is capable of predicting the average number of eggs per spawn and the average number of spawns per female, which was not evaluated previously. The new model is significantly improved in terms of ease of use, platform independence, and utility for providing output in a format that can be used as input into a population dynamics model. Model-predicted minimum and maximum cumulative fecundity over time encompassed the observed data for fadrozole and most propiconazole, prochloraz, fenarimol and trilostane treatments, but did not consistently replicate results from ketoconazole treatments. For average fecundity (eggs•female(-1)•day(-1)), eggs per spawn, and the number of spawns per female, the range of model-predicted values generally encompassed the experimentally observed values. Overall, we

  16. Communication: Ro-vibrational control of chemical reactivity in H+CH₄→ H₂+CH₃: full-dimensional quantum dynamics calculations and a sudden model.

    Science.gov (United States)

    Welsch, Ralph; Manthe, Uwe

    2014-08-07

    The mode-selective chemistry of the title reaction is studied by full-dimensional quantum dynamics simulation on an accurate ab initio potential energy surface for vanishing total angular momentum. Using a rigorous transition state based approach and multi-configurational time-dependent Hartree wave packet propagation, initial state-selected reaction probabilities for many ro-vibrational states of methane are calculated. The theoretical results are compared with experimental trends seen in reactions of methane. An intuitive interpretation of the ro-vibrational control of the chemical reactivity provided by a sudden model based on the quantum transition state concept is discussed.

  17. Personality and intelligence: persistence, not self-directedness, cooperativeness or self-transcendence, is related to twins' cognitive abilities.

    Science.gov (United States)

    Mousavi, Fariba; Rozsa, Sandor; Nilsson, Thomas; Archer, Trevor; Anckarsäter, Henrik; Garcia, Danilo

    2015-01-01

    Background. A person-centered approach focusing on the interaction of an individual's temperament-character-life events is essential in the path of individuals' well-being. In this context, three character traits, Self-directedness (e.g., self-acceptance, self-control, goal-directed behavior), Cooperativeness (e.g., social affiliation, social tolerance, empathy and helpfulness) and Self-transcendence (e.g., spiritual acceptance, transpersonal identification), measured using Cloninger's model of personality are suggested to help the individual to regulate and resolve the conflicts derived from her/his temperament combinations as a reaction to life events. However, if character is related to the individual's cognitive ability, then this association might limit any intervention that focuses on character development. We used data from the Child and Adolescent Twin Study in Sweden (CATSS) to investigate the relationship between personality and cognitive ability. Method. The sample consisted of 370 15-year-old twins (159 girls/211 boys), 192 of whom screen-positive with various types of mental health problems. We used the Temperament and Character Inventory to measure personality and the Wechsler Intelligence Scales for Children (WISC-IV) to measure intelligence. The relationship was investigated using correlation analyses using random-selected twins from each dyad and separately for monozygotic and dizygotic twins. Additional analyses investigated the genetic and environmental effects on personality and cognitive ability in this specific sample. Results. There were no significant correlations between the WISC-IV indices and any of the character traits (i.e., Self-directedness, Cooperativeness, and Self-transcendence). Persistence was significantly related, if weak, to four WISC-IV indices: Verbal Comprehension, Perceptual Reasoning, Working Memory, and the Full WISC-IV Scale. Post-hoc cross-twin/cross-trait analyses showed that the Persistence-cognitive ability

  18. Personality and intelligence: persistence, not self-directedness, cooperativeness or self-transcendence, is related to twins’ cognitive abilities

    Science.gov (United States)

    Mousavi, Fariba; Rozsa, Sandor; Nilsson, Thomas; Archer, Trevor; Anckarsäter, Henrik

    2015-01-01

    Background. A person-centered approach focusing on the interaction of an individual’s temperament-character-life events is essential in the path of individuals’ well-being. In this context, three character traits, Self-directedness (e.g., self-acceptance, self-control, goal-directed behavior), Cooperativeness (e.g., social affiliation, social tolerance, empathy and helpfulness) and Self-transcendence (e.g., spiritual acceptance, transpersonal identification), measured using Cloninger’s model of personality are suggested to help the individual to regulate and resolve the conflicts derived from her/his temperament combinations as a reaction to life events. However, if character is related to the individual’s cognitive ability, then this association might limit any intervention that focuses on character development. We used data from the Child and Adolescent Twin Study in Sweden (CATSS) to investigate the relationship between personality and cognitive ability. Method. The sample consisted of 370 15-year-old twins (159 girls/211 boys), 192 of whom screen-positive with various types of mental health problems. We used the Temperament and Character Inventory to measure personality and the Wechsler Intelligence Scales for Children (WISC-IV) to measure intelligence. The relationship was investigated using correlation analyses using random-selected twins from each dyad and separately for monozygotic and dizygotic twins. Additional analyses investigated the genetic and environmental effects on personality and cognitive ability in this specific sample. Results. There were no significant correlations between the WISC-IV indices and any of the character traits (i.e., Self-directedness, Cooperativeness, and Self-transcendence). Persistence was significantly related, if weak, to four WISC-IV indices: Verbal Comprehension, Perceptual Reasoning, Working Memory, and the Full WISC-IV Scale. Post-hoc cross-twin/cross-trait analyses showed that the Persistence-cognitive ability

  19. Personality and intelligence: persistence, not self-directedness, cooperativeness or self-transcendence, is related to twins’ cognitive abilities

    Directory of Open Access Journals (Sweden)

    Fariba Mousavi

    2015-08-01

    Full Text Available Background. A person-centered approach focusing on the interaction of an individual’s temperament-character-life events is essential in the path of individuals’ well-being. In this context, three character traits, Self-directedness (e.g., self-acceptance, self-control, goal-directed behavior, Cooperativeness (e.g., social affiliation, social tolerance, empathy and helpfulness and Self-transcendence (e.g., spiritual acceptance, transpersonal identification, measured using Cloninger’s model of personality are suggested to help the individual to regulate and resolve the conflicts derived from her/his temperament combinations as a reaction to life events. However, if character is related to the individual’s cognitive ability, then this association might limit any intervention that focuses on character development. We used data from the Child and Adolescent Twin Study in Sweden (CATSS to investigate the relationship between personality and cognitive ability.Method. The sample consisted of 370 15-year-old twins (159 girls/211 boys, 192 of whom screen-positive with various types of mental health problems. We used the Temperament and Character Inventory to measure personality and the Wechsler Intelligence Scales for Children (WISC-IV to measure intelligence. The relationship was investigated using correlation analyses using random-selected twins from each dyad and separately for monozygotic and dizygotic twins. Additional analyses investigated the genetic and environmental effects on personality and cognitive ability in this specific sample.Results. There were no significant correlations between the WISC-IV indices and any of the character traits (i.e., Self-directedness, Cooperativeness, and Self-transcendence. Persistence was significantly related, if weak, to four WISC-IV indices: Verbal Comprehension, Perceptual Reasoning, Working Memory, and the Full WISC-IV Scale. Post-hoc cross-twin/cross-trait analyses showed that the Persistence

  20. Evaluating sulfur dynamics during storm events for three watersheds in the northeastern USA: a combined hydrological, chemical and isotopic approach

    Science.gov (United States)

    Myron J. Mitchell; Scott W. Bailey; James B. Shanley; Bernhard. Mayer

    2008-01-01

    Concerns related to climate change have resulted in an increasing interest in the importance of hydrological events such as droughts in affecting biogeochemical responses of watersheds. The effects of an unusually dry summer in 2002 had a marked impact on the biogeochemistry of three watersheds in the north-eastern USA. Chemical, isotopic and hydrological responses...

  1. Advances in chemical physics, advancing theory for kinetics and dynamics of complex, many-dimensional systems clusters and proteins

    CERN Document Server

    Rice, Stuart A; Komatsuzaki, Tamiki; Berry, R Stephen; Leitner, David M; Rice, Stuart A; Berry, R Stephen Stephen; Leitner, David M M

    2011-01-01

    This series provides the chemical physics field with a forum for critical, authoritative evaluations of advances in every area of the discipline. Volume 145 in the series continues to report recent advances with significant, up-to-date chapters by internationally recognized researchers.

  2. The dynamics of nitrogen derived from a chemical nitrogen fertilizer with treated swine slurry in paddy soil-plant systems.

    Science.gov (United States)

    Lee, Joonhee; Choi, Hong L

    2017-01-01

    A well-managed chemical nitrogen (N) fertilization practice combined with treated swine slurry (TSS) is necessary to improve sustainability and N use efficiency in rice farming. However, little is known about the fate of N derived from chemical N fertilizer with and without TSS in paddy soil-plant systems. The objectives of this study were (1) to estimate the contribution of applied N fertilizer to N turnover in rice paddy soil with different N fertilization practices that were manipulated by the quantity of treated swine slurry and chemical N fertilizer (i.e., HTSS+LAS, a high amount of TSS with a low amount of ammonium sulfate; LTSS+HAS, a low amount of TSS with a high amount of ammonium sulfate; AS, ammonium sulfate with phosphorus and potassium; C, the control) and (2) to compare the rice response to applied N derived from each N fertilization practice. Rice biomass yield, 15N recovery in both rice grain and stems, soil total N (TN), soil inorganic N, and soil 15N recovery were analyzed. Similar amounts of 15N uptake by rice in the TSS+AS plots were obtained, indicating that the effects of the different quantities of TSS on chemical fertilizer N recovery in rice during the experimental period were not significant. The soil 15N recoveries of HTSS+LAS, LTSS+HAS, and AS in each soil layer were not significantly different. For the HTSS+LAS, LTSS+HAS and AS applications, total 15N recoveries were 42%, 43% and 54%, respectively. Because the effects of reducing the use of chemical N fertilizer were attributed to enhancing soil quality and cost-effectiveness, HTSS+LAS could be an appropriate N fertilization practice for improving the long-term sustainability of paddy soil-plant systems. However, N losses, especially through the coupled nitrification-denitrification process, can diminish the benefits that HTSS+LAS offers.

  3. Chemical Imaging and Dynamical Studies of Reactivity and Emergent Behavior in Complex Interfacial Systems. Final Technical Report

    Energy Technology Data Exchange (ETDEWEB)

    Sibener, Steven J. [University of Chicago, IL (United States)

    2014-03-11

    This research program explored the efficacy of using molecular-level manipulation, imaging and scanning tunneling spectroscopy in conjunction with supersonic molecular beam gas-surface scattering to significantly enhance our understanding of chemical processes occurring on well-characterized interfaces. One program focus was on the spatially-resolved emergent behavior of complex reaction systems as a function of the local geometry and density of adsorbate-substrate systems under reaction conditions. Another focus was on elucidating the emergent electronic and related reactivity characteristics of intentionally constructed single and multicomponent atom- and nanoparticle-based materials. We also examined emergent chirality and self-organization in adsorbed molecular systems where collective interactions between adsorbates and the supporting interface lead to spatial symmetry breaking. In many of these studies we combined the advantages of scanning tunneling (STM) and atomic force (AFM) imaging, scanning tunneling local electronic spectroscopy (STS), and reactive supersonic molecular beams to elucidate precise details of interfacial reactivity that had not been observed by more traditional surface science methods. Using these methods, it was possible to examine, for example, the differential reactivity of molecules adsorbed at different bonding sites in conjunction with how reactivity is modified by the local configuration of nearby adsorbates. At the core of this effort was the goal of significantly extending our understanding of interfacial atomic-scale interactions to create, with intent, molecular assemblies and materials with advanced chemical and physical properties. This ambitious program addressed several key topics in DOE Grand Challenge Science, including emergent chemical and physical properties in condensed phase systems, novel uses of chemical imaging, and the development of advanced reactivity concepts in combustion and catalysis including carbon

  4. Accurate calculation of chemical shifts in highly dynamic H2@C60 through an integrated quantum mechanics/molecular dynamics scheme.

    Science.gov (United States)

    Jiménez-Osés, Gonzalo; García, José I; Corzana, Francisco; Elguero, José

    2011-05-20

    A new protocol combining classical MD simulations and DFT calculations is presented to accurately estimate the (1)H NMR chemical shifts of highly mobile guest-host systems and their thermal dependence. This strategy has been successfully applied for the hydrogen molecule trapped into C(60) fullerene, an unresolved and challenging prototypical case for which experimental values have never been reproduced. The dependence of the final values on the theoretical method and their implications to avoid over interpretation of the obtained results are carefully described.

  5. Supporting interpretation of dynamic simulation. Application to chemical kinetic models; Aides a l`interpretation de simulations dynamiques. Application aux modeles de cinetique chimique

    Energy Technology Data Exchange (ETDEWEB)

    Braunschweig, B.

    1998-04-22

    Numerous scientific and technical domains make constant use of dynamical simulations. Such simulators are put in the hands of a growing number of users. This phenomenon is due both to the extraordinary increase in computing performance, and to better graphical user interfaces which make simulation models easy to operate. But simulators are still computer programs which produce series of numbers from other series of numbers, even if they are displayed graphically. This thesis presents new interaction paradigms between a dynamical simulator and its user. The simulator produces a self-made interpretation of its results, thanks to a dedicated representation of its domain with objects. It shows dominant cyclic mechanisms identified by their instantaneous loop gain estimates, it uses a notion of episodes for splitting the simulation into homogeneous time intervals, and completes this by animations which rely on the graphical structure of the system. These new approaches are demonstrated with examples from chemical kinetics, because of the energic and exemplary characteristics of the encountered behaviors. They are implemented in the Spike software, Software Platform for Interactive Chemical Kinetics Experiments. Similar concepts are also shown in two other domains: interpretation of seismic wave propagation, and simulation of large projects. (author) 95 refs.

  6. Aesthetics of Otherness:Variation of Transcendence and Intersubjectivity%他者性的美学:超越性与主体间性的变异

    Institute of Scientific and Technical Information of China (English)

    杨春时

    2012-01-01

    他者性美学是在他者性哲学的基础上形成的。列维纳斯从他者的超越性出发,把审美界定为超越经验意识的感觉,把美确定为物的本原状态。这样,他的美学就具有自然主义的倾向,而否认了审美的超越性。同时,他认为美只是"物"的还原,它超越于存在,因此不是主体,也不是人的对象,与人无关。这一思想固然摆脱了主体性,但也否定了审美的主体间性。另一个他者性美学家路易斯认为,审美源于道,道是他者,具有伦理性。艺术的他者性体现在语言、文本、创作、接受各个环节,因此审美具有公共性、客观性,而不是主体性的活动。这一理论使审美的超越性和主体间性发生了变异。从本质上说,他者性美学对他者的超越性和非主体性的强调,实际上是超越性和主体间性理论的扭曲形式。在这个意义上,他者性美学的发生,为肯定审美的主体间性和超越性开辟了道路。%Aesthetics of otherness is formed on the basis of philosophy of otherness.Starting from the transcendence of others,Levinas defined aesthetics as the sense of transcending empirical consciousness and beauty as the primary state of things.Thus done,he gave a naturalistic tendency to his aesthetics,denying transcendence of beauty appreciation.Meanwhile,he believed that beauty was reduction of "things" and transcended existence,so it had nothing to do with men,neither as the subject nor as the object of men.Although his idea broke away from subjectivity,it denied intersubjectivity in beauty appreciation.Louis,another aesthetician of otherness,thought that beauty appreciation originated from Tao,which was the other and ethical.Artistic otherness gives expression to language,text,writing and reception.Thus,beauty appreciation is not a subjective,but public and objective activity.This theory brought about variation to aesthetic transcendence and intersubjectivity.In essence,aesthetics of

  7. Chemical Modification: an Effective Way of Avoiding the Collapse of SWNTs on Al Surface Revealed by Molecular Dynamics Simulations

    DEFF Research Database (Denmark)

    Xie, J.; Xue, Q. Z.; Yan, K. Y.

    2009-01-01

    The rapid collapse of intrinsic single-walled carbon nanotube (SWNT) on the aluminum surface is observed using molecular dynamics simulation. The collapsing threshold is similar to 10 angstrom, and the length has no influence on its collapse. Furthermore, we report that the structural stability...

  8. A sequence in subdomain 2 of DBL1α of Plasmodium falciparum erythrocyte membrane protein 1 induces strain transcending antibodies.

    Directory of Open Access Journals (Sweden)

    Karin Blomqvist

    Full Text Available Immunity to severe malaria is the first level of immunity acquired to Plasmodium falciparum. Antibodies to the variant antigen PfEMP1 (P. falciparum erythrocyte membrane protein 1 present at the surface of the parasitized red blood cell (pRBC confer protection by blocking microvascular sequestration. Here we have generated antibodies to peptide sequences of subdomain 2 of PfEMP1-DBL1α previously identified to be associated with severe or mild malaria. A set of sera generated to the amino acid sequence KLQTLTLHQVREYWWALNRKEVWKA, containing the motif ALNRKE, stained the live pRBC. 50% of parasites tested (7/14 were positive both in flow cytometry and immunofluorescence assays with live pRBCs including both laboratory strains and in vitro adapted clinical isolates. Antibodies that reacted selectively with the sequence REYWWALNRKEVWKA in a 15-mer peptide array of DBL1α-domains were also found to react with the pRBC surface. By utilizing a peptide array to map the binding properties of the elicited anti-DBL1α antibodies, the amino acids WxxNRx were found essential for antibody binding. Complementary experiments using 135 degenerate RDSM peptide sequences obtained from 93 Ugandan patient-isolates showed that antibody binding occurred when the amino acids WxLNRKE/D were present in the peptide. The data suggests that the ALNRKE sequence motif, associated with severe malaria, induces strain-transcending antibodies that react with the pRBC surface.

  9. 'Thinking ill of others without sufficient warrant?' Transcending the accuracy-inaccuracy dualism in prejudice and stereotyping research.

    Science.gov (United States)

    Dixon, John

    2017-03-01

    Research on prejudice seeks to understand and transform inaccurate beliefs about others. Indeed, historically such research has offered a cautionary tale of the biased nature of human cognition. Recently, however, this view has been challenged by work defending the essential rationality of intergroup perception, a theme captured controversially in Jussim and colleagues' (2009) research on the 'unbearable accuracy of stereotyping'. The present paper argues that in its own terms the 'rationalist turn' in socio-cognitive research on stereotyping presents an important challenge to the prejudice tradition, raising troubling questions about its conceptual and empirical foundations. However, it also argues for the necessity of transcending those terms. By focusing on the correspondence between individual beliefs and the supposedly 'objective' characteristics of others, we neglect the historical and discursive practices through which the social realities that we 'perceive' are actively constructed and institutionalized. We mask their social origins, contested and perspectival nature, relativity, and relationship to wider structures of power. By implication, moving beyond the Allportian perspective that has dominated both the prejudice tradition and the emerging stereotype accuracy paradigm, we may now need to prioritize other kinds of questions. Reversing Allport's famous definition of prejudice, it may now be time to ask: How, and with what consequences, does 'thinking ill of others' become sufficiently warranted? How does such thinking become part of institutionalized relations of power and an accepted way of perceiving, evaluating and treating others? What should social psychologists be doing to challenge this state of affairs? © 2017 The British Psychological Society.

  10. Strain-transcending immune response generated by chimeras of the malaria vaccine candidate merozoite surface protein 2

    Science.gov (United States)

    Krishnarjuna, Bankala; Andrew, Dean; MacRaild, Christopher A.; Morales, Rodrigo A. V.; Beeson, James G.; Anders, Robin F.; Richards, Jack S.; Norton, Raymond S.

    2016-01-01

    MSP2 is an intrinsically disordered protein that is abundant on the merozoite surface and essential to the parasite Plasmodium falciparum. Naturally-acquired antibody responses to MSP2 are biased towards dimorphic sequences within the central variable region of MSP2 and have been linked to naturally-acquired protection from malaria. In a phase IIb study, an MSP2-containing vaccine induced an immune response that reduced parasitemias in a strain-specific manner. A subsequent phase I study of a vaccine that contained both dimorphic forms of MSP2 induced antibodies that exhibited functional activity in vitro. We have assessed the contribution of the conserved and variable regions of MSP2 to the generation of a strain-transcending antibody response by generating MSP2 chimeras that included conserved and variable regions of the 3D7 and FC27 alleles. Robust anti-MSP2 antibody responses targeting both conserved and variable regions were generated in mice, although the fine specificity and the balance of responses to these regions differed amongst the constructs tested. We observed significant differences in antibody subclass distribution in the responses to these chimeras. Our results suggest that chimeric MSP2 antigens can elicit a broad immune response suitable for protection against different strains of P. falciparum. PMID:26865062

  11. Subverting the pastoral: the transcendence of space and place in J.M. Coetzee’s Disgrace

    Directory of Open Access Journals (Sweden)

    S. Smit-Marais

    2006-07-01

    Full Text Available This article investigates how J.M. Coetzee’s “Disgrace” (1999 – portrayed as a postcolonial and postmodern fictional event – embodies, problematises and subverts the vision of the pastoral farm novel tradition by transcending traditional configurations of space and place. The novel offers a rather bleak apocalyptic vision of gender roles, racial relationships and family relations in post-apartheid South Africa and expresses the socio-political tensions pertaining to the South African landscape in terms of personal relationships. As a fictional reworking of the farm novel, “Disgrace” draws on the tradition’s anxieties about the rights of (white ownership, but within a post-apartheid context. As such, “Disgrace” challenges the pastoral farm novel’s “dream topography” (Coetzee, 1988:6 of the family farm ruled by the patriarch – a topography inscribed – with the help of the invisible labour of black hands – as a legacy of power and ownership to be inherited and cultivated in perpetuity. Accordingly, the concept “farm” is portrayed as a contested and liminal space inscribed with a history of violence and dispossession – a dystopia. This article therefore conceptualises “Disgrace” as an antipastoral farm novel that reconfigures the concept “farm” – within the context of the South African reality – by subverting, inverting and parodying the structures of space and place postulated by the pastoral farm novel.

  12. Consumer participation in co-creation: An enlightening model of causes and effects based on ethical values and transcendent motives

    Directory of Open Access Journals (Sweden)

    Ricardo eMartinez Cañas

    2016-05-01

    Full Text Available In the highly interconnected modern world, the role of consumers has changed substantially due to their collaboration with companies in generating ideas, products, and services, as well as their increasing engagement with social values. Specifically, consumer participation has become key to the development of successful products and services. With an integrative review of research into value co-creation and ethics, this article proposes a conceptual model in which consumers’ ethical values and transcendent motivations encourage their engagement in co-creation activities. In this new paradigm, the co-creation process can be a means to emphasize the social and moral aspects of co-creating. This article identifies important value benefits attained by both companies and consumers after consumers engage in co-creation activities, and highlights that these benefits increase when ethical products are the object of these co-creation activities. It also notes the important, supportive role of the Marketing 3.0 paradigm and Web 3.0 tools to initiate the co-creating process. All these insights have notable implications for both research and managerial practice.

  13. Empatia e Transcendência: Reflexões sobre o Sistema Filosófico de Quine

    Directory of Open Access Journals (Sweden)

    Vera Vidal

    2003-12-01

    Full Text Available The aim of this paper is to show some of my contributions to the exegesis of Quine’s philosophy, emphasizing the role played by notions such as empathy and transcendence in his philosophical system. I hold that Quine is a rigorous systematic philosopher, and that in order to understand each one of his theses and critiques we need to analyze them within the totality of his philosophical investigations. I believe that his system derives from what we call his epistemological project and that all his philosophical theses are founded in his theory of language learning. I also maintain that Quine’s philosophy shows a very strong pragmatic aspect more closely related to Wittgenstein’s tradition and that one of speech acts theorists than to the Skinnerian tradition with which Quine is often associated. In addition I believe that the overall position of his theses has been presented in Word and Object, and that all his subsequent works served to clarify or complement his ideas, not to change them. Thus, I do not agree with those who argue that Quine changed his philosophical position in the course of time.

  14. The induction of a radiation-induced bystander effect in fish transcends taxonomic group and trophic level.

    Science.gov (United States)

    Smith, Richard W; Seymour, Colin B; Moccia, Richard D; Hinton, Thomas G; Mothersill, Carmel E

    2013-04-01

    To extend the investigations of bystander effect induction in fish of the same species as the irradiated fish, to bystander effect induction between fish species and between trophic levels. To investigate interspecies bystander effect induction, zebrafish and medaka were irradiated with a 0.5 Gy X-ray dose and then swum with non-irradiated fish of the same and opposite species. To investigate trophic level bystander effect induction, California blackworms were irradiated with the same X-ray dose and then fed to non-irradiated rainbow trout. Reductions in clonogenic survival of the HPV-G (non-transformed human keratinocytes, immortalized with the human papilloma virus) reporter cell line, treated with tissue explant media, revealed that zebrafish and medaka induced a pro-apoptotic bystander effect in the other species and that, in trout, the normally anti-apoptotic effect caused by the consumption of non-irradiated blackworms was significantly reduced or lost if the blackworms had been irradiated. These results are the first to show that a radiation- induced bystander effect can transcend taxonomic group and trophic level in fish. This provides further evidence that bystander signals are widespread and conserved and may be transmitted through an ecosystem, as well as between individuals of the same species.

  15. An integrated ion trap and time-of-flight mass spectrometer for chemical and photo- reaction dynamics studies.

    Science.gov (United States)

    Schowalter, Steven J; Chen, Kuang; Rellergert, Wade G; Sullivan, Scott T; Hudson, Eric R

    2012-04-01

    We demonstrate the integration of a linear quadrupole trap with a simple time-of-flight mass spectrometer with medium-mass resolution (m/Δm ∼ 50) geared towards the demands of atomic, molecular, and chemical physics experiments. By utilizing a novel radial ion extraction scheme from the linear quadrupole trap into the mass analyzer, a device with large trap capacity and high optical access is realized without sacrificing mass resolution. This provides the ability to address trapped ions with laser light and facilitates interactions with neutral background gases prior to analyzing the trapped ions. Here, we describe the construction and implementation of the device as well as present representative ToF spectra. We conclude by demonstrating the flexibility of the device with proof-of-principle experiments that include the observation of molecular-ion photodissociation and the measurement of trapped-ion chemical reaction rates. © 2012 American Institute of Physics

  16. Are ACE-inhibitors or ARB's still needed for cardiovascular prevention in high risk patients? Insights from PRoFESS and TRANSCEND

    OpenAIRE

    Van Mieghem, W; Billiouw, J.-M.; Brohet, C; Dupont, A. G.; Gazagnes, M.-D.; Heller, F.; Krzesinski, Jean-Marie; Missault, L; Persu, A; Pierard, Luc; Rottiers, R.; VANHOOREN G.; Vervaet, P.; Herman, A. G.

    2010-01-01

    The HOPE and EUROPA clinical studies have shown that treatment with the angiotensin-converting enzyme (ACE) inhibitors, ramipril and perindopril, may reduce the occurence of major cardiovascular events in patients with proven atherosclerotic disease. The recently published results of the PRoFESS and TRANSCEND trials completed the much needed information concerning the use of an angiotensin receptor blocker for patients at high risk of cardiovascular events. PRoFESS compared a therapy of tel...

  17. Dynamic stiffness of chemically and physically ageing rubber vibration isolators in the audible frequency range. Part 1: constitutive equations

    Science.gov (United States)

    Kari, Leif

    2017-09-01

    The constitutive equations of chemically and physically ageing rubber in the audible frequency range are modelled as a function of ageing temperature, ageing time, actual temperature, time and frequency. The constitutive equations are derived by assuming nearly incompressible material with elastic spherical response and viscoelastic deviatoric response, using Mittag-Leffler relaxation function of fractional derivative type, the main advantage being the minimum material parameters needed to successfully fit experimental data over a broad frequency range. The material is furthermore assumed essentially entropic and thermo-mechanically simple while using a modified William-Landel-Ferry shift function to take into account temperature dependence and physical ageing, with fractional free volume evolution modelled by a nonlinear, fractional differential equation with relaxation time identical to that of the stress response and related to the fractional free volume by Doolittle equation. Physical ageing is a reversible ageing process, including trapping and freeing of polymer chain ends, polymer chain reorganizations and free volume changes. In contrast, chemical ageing is an irreversible process, mainly attributed to oxygen reaction with polymer network either damaging the network by scission or reformation of new polymer links. The chemical ageing is modelled by inner variables that are determined by inner fractional evolution equations. Finally, the model parameters are fitted to measurements results of natural rubber over a broad audible frequency range, and various parameter studies are performed including comparison with results obtained by ordinary, non-fractional ageing evolution differential equations.

  18. 化学工业园的系统动力学仿真与调控%Simulation and Adjustment of System Dynamics for a Chemical Industrial Park

    Institute of Scientific and Technical Information of China (English)

    郑斯瑞; 钱新; 瞿庆玲

    2011-01-01

    化学工业园属行业类工业园,入区企业主要为生产和销售化学工业品的化工企业,其排放的化学品污染物极易造成水环境和大气环境质量的恶化,为避免环境风险事故,必须对化学工业园的发展过程进行模拟和控制.以泰兴经济开发区为研究对象,在其现阶段发展基础上,根据该园区的实际情况,采用系统动力学(System Dynamics)模拟不同情景下的远期发展目标.基础仿真结果表明,泰兴经济开发区的环境现状不容乐观,尤其是大气环境污染几乎达到环境容量极限.情景分析表明,该开发园区必须将产业发展速度控制在 18%,同时降低工业能耗,提高脱硫效率至 90%以上,污水处理厂规模日处理量达 4.9×10t,才能保证其持续、稳定、健康的发展.%Chemical industrial parks, a type of industrial park, mainly consist of chemical enterprises which produce and sell chemical industrial products. Their chemical pollution-containing emissions tend to cause water and air environmental quality degradation. To avoid environmental accidents, it is necessary to simulate and control the whole development process of chemical industrial parks. Using Taixing economic development zone as an example, long-term goals based on the current situation were simulated under different scenarios through applying system dynamics. The base runs tell us that the current environmental quality of the park is far from optimistic, especially the air pollution, which has almost reached the environmental capacity limit. Scenario analysis shows that to maintain sustainable development during the planning period, the development speed should be 18%.Simultaneously, energy consumption should be lowered, desulphurization efficiency should be improved to above 90% , and the capacity of the sewage treatment plants should reach 4.9 × 104 t/d.

  19. All-atom Molecular Dynamic Simulations Combined with the Chemical Shifts Study on the Weak Interactions of Ethanol-water System

    Institute of Scientific and Technical Information of China (English)

    ZHANG Rong; LUO San-Lai; WU Wen-Juan

    2008-01-01

    All-atom molecular dynamics(MD)simulation combined with chemical shifts was performed to investigate the interactions over the entire concentration range of the ethanol(EtOH)-water system.The results of the simulation were adopted to explain the NMR experiments by hydrogen bonding analysis.The strong hydrogen bonds and weak C-H…O contacts coexist in the mixtures through the analysis of the radial distribution functions.And the liquid structures in the whole concentration of EtOH-water mixtures can be classified into three regions by the statistic analysis of the hydrogen-bonding network in the MD simulations.Moreover,the chemical shifts of the hydrogen atom are in agreement witb the statistical results of the average number hydrogen bonds in the MD simulations.Interestingly,the excess relative extent Eηrel calculated by the MD simulations and chemical shifts in the EtOH aqueous solutions shows the largest deviation at XEtOH≈0.18.The excess properties present good agreement with the excess enthalpy in the concentration dependence.

  20. Uma reflexão sobre a importância da transcendência e dos mitos para as religiões a partir do episódio da reforma de Amarna, no antigo Egito / A reflection on the importance of transcendence and myths for religions on the basis of the Amarna reform episode, in ancient Egypt

    Directory of Open Access Journals (Sweden)

    Ciro Flamarion Cardoso

    2011-05-01

    Full Text Available This text endeavours to study the period of the Amarnian reform in ancient Egypt, in the light of the still available primary sources (written and iconographic and on the basis of two hypotheses about the nature of that reform, namely the elimination of any transcendence and that of the mythical form of thought. The results of such decisions show, through the failure of the reform attempted by the pharaoh Akhenaten, that transcendence and myths are enormously important for any religious thought.Este texto aborda, à luz das fontes primárias disponíveis (escritas e iconográficas, o período da reforma amarniana no antigo Egito, a partir de duas hipóteses sobre o que seria o caráter central dessa reforma, isto é, a eliminação de qualquer transcendência e aquela do pensamento mítico. As consequências de tais decisões mostram, mediante o fracasso da reforma tentada pelo faraó Akhenaton, a enorme importância da transcendência e dos mitos para o pensamento religioso.

  1. Insight into the effect of inhibitor resistant S130G mutant on physico-chemical properties of SHV type beta-lactamase: a molecular dynamics study.

    Directory of Open Access Journals (Sweden)

    Mohd Hassan Baig

    Full Text Available Bacterial resistance is a serious threat to human health. The production of β-lactamase, which inactivates β-lactams is most common cause of resistance to the β-lactam antibiotics. The Class A enzymes are most frequently encountered among the four β-lactamases in the clinic isolates. Mutations in class A β-lactamases play a crucial role in substrate and inhibitor specificity. SHV and TEM type are known to be most common class A β-lactamases. In the present study, we have analyzed the effect of inhibitor resistant S130G point mutation of SHV type Class-A β-lactamase using molecular dynamics and other in silico approaches. Our study involved the use of different in silico methods to investigate the affect of S130G point mutation on the major physico-chemical properties of SHV type class A β-lactamase. We have used molecular dynamics approach to compare the dynamic behaviour of native and S130G mutant form of SHV β-lactamase by analyzing different properties like root mean square deviation (RMSD, H-bond, Radius of gyration (Rg and RMS fluctuation of mutation. The results clearly suggest notable loss in the stability of S130G mutant that may further lead to decrease in substrate specificity of SHV. Molecular docking further indicates that S130G mutation decreases the binding affinity of all the three inhibitors in clinical practice.

  2. Chiral recognition of Propranolol enantiomers by β-Cyclodextrin: Quantum chemical calculation and molecular dynamics simulation studies

    Energy Technology Data Exchange (ETDEWEB)

    Ghatee, Mohammad Hadi, E-mail: ghatee@susc.ac.ir; Sedghamiz, Tahereh

    2014-12-05

    Highlights: • Enantiomeric recognition of Propranolol studied by β-Cyclodextrin complexations. • Complexes characterized by PM3 and molecular dynamics (MD) simulation methods. • Results support more stability of R-enantiomer complex in gas and in aqueous solution phases. • Gas phase complexes are unlikely free-energy-wise, though solution phase’s are more likely. • Higher molecular diffusion in aqueous solution phase is inherent to S-enantiomer. - Abstract: Enantiomeric recognition of Propranolol by complexation with β-Cyclodextrin was studied by PM3 method and molecular dynamics (MD) simulation. Gas phase results show that the R-enantiomer complex is more stable than the S-enantiomer complex by 8.54 kJ/mol (Hartree–Fock energy). Using polarized continuum model, solution phase of R-enantiomer complex was found to be more stable than S-enantiomer complex by 25.95 kJ/mol. Both complexes hardly occur at room temperature free-energy-wise, though, complexation with R-enantiomer is more favorable than with S-enantiomer enthalpy-wise. Also, complexes were studied by molecular dynamics simulation in gas and solution phases. More stability of R-enantiomer complex in gas phase is confirmed by MD van der Waals energy (5.04 kJ/mol) and closely by the counterpart PM3 binding energy (8.54 kJ/mol). Simulation in solution phase indicates more stability of R-enantiomer complex. Finally, simulated transport property provides insight into the high anisotropic atoms motion according to which S-Propranolol found possessing significantly higher dynamics.

  3. Chiral recognition of Propranolol enantiomers by β-Cyclodextrin: Quantum chemical calculation and molecular dynamics simulation studies

    Science.gov (United States)

    Ghatee, Mohammad Hadi; Sedghamiz, Tahereh

    2014-12-01

    Enantiomeric recognition of Propranolol by complexation with β-Cyclodextrin was studied by PM3 method and molecular dynamics (MD) simulation. Gas phase results show that the R-enantiomer complex is more stable than the S-enantiomer complex by 8.54 kJ/mol (Hartree-Fock energy). Using polarized continuum model, solution phase of R-enantiomer complex was found to be more stable than S-enantiomer complex by 25.95 kJ/mol. Both complexes hardly occur at room temperature free-energy-wise, though, complexation with R-enantiomer is more favorable than with S-enantiomer enthalpy-wise. Also, complexes were studied by molecular dynamics simulation in gas and solution phases. More stability of R-enantiomer complex in gas phase is confirmed by MD van der Waals energy (5.04 kJ/mol) and closely by the counterpart PM3 binding energy (8.54 kJ/mol). Simulation in solution phase indicates more stability of R-enantiomer complex. Finally, simulated transport property provides insight into the high anisotropic atoms motion according to which S-Propranolol found possessing significantly higher dynamics.

  4. Chemical heat pumping - a rapid experimental procedure for investigating the suitability of salt hydrates under dynamic conditions

    Energy Technology Data Exchange (ETDEWEB)

    Andersson, Jan; Azoulay, Michel; Pablo, J. de

    A rapid experimental procedure of interest in determining the suitability of salt hydrates to be used in chemical heat pumping is described. Thermogravimetry under controlled water vapour pressure is utilized as the key diagnostic method. The test procedure relies largely on two critical tests: a cycling and an inhibition test. The former gives information on the stoichiometric reversibility and hysteresis between the dehydration and rehydration branches, while the inhibition test yields more quantitative information about the extent of inhibition. The latter represents a source of irreversibility inherent to the salt hydrate system. The test procedure is discussed and illustrated using four different salt hydrates: barium chloride, sodium sulphide, magnesium chloride and lithium hydroxide.

  5. Dynamic Modeling and Plantwide Control of a Hybrid Power and Chemical Plant: An Integrated Gasification Combined Cycle Coupled with a Methanol Plant

    Science.gov (United States)

    Robinson, Patrick J.

    simulators Aspen Plus and Aspen Dynamics. This dissertation first presents a simple approximate method for achieving the objective of having a gasifier model that can be exported into Aspen Dynamics. Limitations in the software dealing with solids make this a necessary task. The basic idea is to use a high molecular weight hydrocarbon that is present in the Aspen library as a pseudo fuel. For many plantwide dynamic studies, a rigorous high-fidelity dynamic model of the gasifier is not needed because its dynamics are very fast and the gasifier gas volume is a relatively small fraction of the total volume of the entire plant. The proposed approximate model captures the essential macro-scale thermal, flow, composition and pressure dynamics. This paper does not attempt to optimize the design or control of gasifiers, but merely presents an idea of how to dynamically simulate coal gasification in an approximate way. This dissertation also presents models of the downstream units of a typical IGCC. Dynamic simulations of the H2S absorption/stripping unit, Water-gas Shift (WGS) reactors, and CO2 absorption/stripping unit are essential for the development of stable and agile plantwide control structures of this hybrid power/chemical plant. Due to the high pressure of the system, hydrogen sulfide is removed by means of physical absorption. SELEXOLRTM (a mixture of the dimethyl ethers of polyethylene glycol) is used to achieve a gas purity of less than 5 ppm H2S. This desulfurized synthesis gas is sent to two water gas shift reactors that convert a total of 99% of carbon monoxide to hydrogen. Physical absorption of carbon dioxide with Selexol produces a hydrogen rich stream (90 mol% H2) to be fed into combustion turbines or to a methanol plant. Steady-state economic designs and plantwide control structures are developed in this dissertation. A steady-state economic design, control structure, and successful turndown of the methanol plant are shown in this dissertation. The Plantwide

  6. From the Conceptual Change Model to the Productive Ecological Koinos Model: Learning that transcends

    Science.gov (United States)

    Gelpi-Rodriguez, Phaedra

    This investigation presents the analysis of a model of teaching science called the Conceptual Change Model. This model stimulates students to identify their own and alternate science concepts, and to confront these concepts with dynamic situations that will incite a conceptual change and promote their ability to master and understand the conceptual systems that serve as foundations for scientific knowledge. During a previous research made by this investigator on the Conceptual Change Model, a proposal for a new teaching model came up which she called the Productive Ecological Koinos Model. This model incorporates, among other things, the teacher's reflection and inner thoughts about the concepts taught and the learning experiences achieved in concurrence with students. Using action research, an exploration and analysis was done that focused upon how students and teachers modified their perspective of science while testing the Productive Ecological Koinos Model during the teaching-learning processes that took place in a microbiology course. The action research design allows the researcher to analyze these points from the experiential perspective, while also allowing the researcher to participate in the study. The study employed qualitative research techniques such as reflective diaries, personal profiles of participants, document analysis, audio tape recordings and transcriptions. All of these techniques are accepted within action research (Elliot, 1991). The Wolcott Model was the data analysis method used in the research. The description, analysis and interpretation carried out allowed for the examination of the various components of the Productive Ecological Koinos Model with students and teachers as to the scientific terms virus and contagion, and their experiences during the learning process within and outside the classroom. From the analysis of the Model a modification cropped up which places emphasis on conscious introspection on the learning process. This new

  7. Dynamic neurotransmitter interactions measured with PET

    Energy Technology Data Exchange (ETDEWEB)

    Schiffer, W.K.; Dewey, S.L.

    2001-04-02

    Positron emission tomography (PET) has become a valuable interdisciplinary tool for understanding physiological, biochemical and pharmacological functions at a molecular level in living humans, whether in a healthy or diseased state. The utility of tracing chemical activity through the body transcends the fields of cardiology, oncology, neurology and psychiatry. In this, PET techniques span radiochemistry and radiopharmaceutical development to instrumentation, image analysis, anatomy and modeling. PET has made substantial contributions in each of these fields by providing a,venue for mapping dynamic functions of healthy and unhealthy human anatomy. As diverse as the disciplines it bridges, PET has provided insight into an equally significant variety of psychiatric disorders. Using the unique quantitative ability of PET, researchers are now better able to non-invasively characterize normally occurring neurotransmitter interactions in the brain. With the knowledge that these interactions provide the fundamental basis for brain response, many investigators have recently focused their efforts on an examination of the communication between these chemicals in both healthy volunteers and individuals suffering from diseases classically defined as neurotransmitter specific in nature. In addition, PET can measure the biochemical dynamics of acute and sustained drug abuse. Thus, PET studies of neurotransmitter interactions enable investigators to describe a multitude of specific functional interactions in the human brain. This information can then be applied to understanding side effects that occur in response to acute and chronic drug therapy, and to designing new drugs that target multiple systems as opposed to single receptor types. Knowledge derived from PET studies can be applied to drug discovery, research and development (for review, see (Fowler et al., 1999) and (Burns et al., 1999)). Here, we will cover the most substantial contributions of PET to understanding

  8. Structural Characterization of Self-Assembled Monolayers of Organosilanes Chemically Bonded on Silica Wafers by Dynamical Force Microscopy

    CERN Document Server

    Navarre, S; Bousbaa, J; Bennetau, B; Nony, L; Aimé, J P; Choplin, Franck; Bennetau, Bernard; Nony, Laurent; Aim\\'{e}, Jean-Pierre

    2001-01-01

    In this article, a dynamical force microscopy study of self-assembled monolayers of organosilanes, grafted on a silica support, is reported. Organosilanes, terminated either with a functional group (ethylene glycol) or with a methyl group, were used. The influence of the reaction time and the solvent composition on the grafting was investigated to improve the homogeneity of the self-assembled monolayers. Numerical simulations of approach-retract curves, obtained in the tapping mode, were performed and compared to experimental ones. Informations, such as mechanical response and height of the grafted organic layers, have been obtained.

  9. Consumer Participation in Co-creation: An Enlightening Model of Causes and Effects Based on Ethical Values and Transcendent Motives.

    Science.gov (United States)

    Martínez-Cañas, Ricardo; Ruiz-Palomino, Pablo; Linuesa-Langreo, Jorge; Blázquez-Resino, Juan J

    2016-01-01

    In the current highly interconnected modern world, the role of consumers has changed substantially due to their active collaboration with companies in product and process innovation. Specifically, consumer participation has become key to the development of successful products and services, as companies have come to rely more and more on consumers' opinion as a source of innovative ideas and brand value. However, whereas existing research has focused on identifying the different elements involved in consumers' co-creation, there is still the need to comprehend better this complex mechanism by integrating distinct dimensional insights. With an integrative review of research into three important perspectives, one nurturing from the Service-Dominant logic, another one based on the information and communication technologies (ICTs) platforms, and (the ethical values-driven) Marketing 3.0 paradigm, this article proposes a conceptual framework in which consumers' ethical values and transcendent motivations play an important role in encouraging their engagement in co-creation activities. In this connection, and with consumers increasingly embracing the need to fulfill a social and ethical function in society, the co-creation process is here comprehended as a means to emphasize the social and moral aspects of co-creation. This article also identifies the important, supportive role of the Marketing 3.0 paradigm and Web 3.0 tools to initiate the co-creation process, as well as the important valuable benefits attained by both companies and consumers after consumers engage in this process. Importantly, these benefits are highlighted to increase when ethical products are the object of these co-creation activities. All these insights have notable implications for both research and managerial practice.

  10. Transcending the Self – the Illusion of Body Ownership in Immersive Virtual Reality and its Impact on Behaviour

    Directory of Open Access Journals (Sweden)

    Mel Slater

    2011-10-01

    Full Text Available Virtual reality in various forms has been around for about 40 years. It has been considered mainly as a technology that can be used to generate the illusion of a transformation of place. However, it has recently been shown that it can successfully be used to transcend the self, through illusions of body ownership and transformation. Several papers have shown that it is possible to generate in people the illusory sense of ownership of a fake body using virtual reality techniques [1-5]. This can be achieved through synchronous multisensory stimulation with respect to the real and virtual body. For example, the participant sees his or her virtual body touched, while feeling the touch synchronously and in the same place on the real body. This can also lead to illusions of body transformation, such as a thin person having the illusion of being fat [6]. Our research suggests the prime importance of a first person perspective for the illusion of ownership, however, in [7] we also found that a representation of a person in a virtual mirror with synchronous visual-motor effects also results in a body ownership illusion. Although virtual body ownership has been established, what is also of interest are the consequences of this in terms of the attitudes and behaviour of the participant who experiences the transformed body. Our very recent work suggests that the illusion of ownership of a virtual body may also result in at least short-term transformations of behaviour and attitudes of the participant towards those that are appropriate to the virtual body. This talk will describe several experiments illustrating both the illusion of body ownership and its transformative effect on attitudes and behaviour.

  11. Consumer Participation in Co-creation: An Enlightening Model of Causes and Effects Based on Ethical Values and Transcendent Motives

    Science.gov (United States)

    Martínez-Cañas, Ricardo; Ruiz-Palomino, Pablo; Linuesa-Langreo, Jorge; Blázquez-Resino, Juan J.

    2016-01-01

    In the current highly interconnected modern world, the role of consumers has changed substantially due to their active collaboration with companies in product and process innovation. Specifically, consumer participation has become key to the development of successful products and services, as companies have come to rely more and more on consumers' opinion as a source of innovative ideas and brand value. However, whereas existing research has focused on identifying the different elements involved in consumers' co-creation, there is still the need to comprehend better this complex mechanism by integrating distinct dimensional insights. With an integrative review of research into three important perspectives, one nurturing from the Service-Dominant logic, another one based on the information and communication technologies (ICTs) platforms, and (the ethical values-driven) Marketing 3.0 paradigm, this article proposes a conceptual framework in which consumers' ethical values and transcendent motivations play an important role in encouraging their engagement in co-creation activities. In this connection, and with consumers increasingly embracing the need to fulfill a social and ethical function in society, the co-creation process is here comprehended as a means to emphasize the social and moral aspects of co-creation. This article also identifies the important, supportive role of the Marketing 3.0 paradigm and Web 3.0 tools to initiate the co-creation process, as well as the important valuable benefits attained by both companies and consumers after consumers engage in this process. Importantly, these benefits are highlighted to increase when ethical products are the object of these co-creation activities. All these insights have notable implications for both research and managerial practice. PMID:27303349

  12. Dynamic scaling and optical properties of Zn(S, O,OH) thin film grown by chemical bath deposition

    Institute of Scientific and Technical Information of China (English)

    Zhang Yi; Li Bo-Yan; Dang Xiang-Yu; Wu Li; Jin Jing; Li Feng-Yan; Ao Jian-Ping; Sun Yun

    2011-01-01

    The scaling behavior and optical properties of Zn(S,O and OH) thin films deposited on soda-lime glass substrates by chemical bath deposition method were studied by combined roughness measurements,scanning electron microscopy and optical properties measurement.From the scaling behaviour,the value of growth scaling exponent β,0.38±0.06,was determined.This value indicated that the Zn(S,O,OH) film growth in the heterogeneous process was influenced by the surface diffusion and shadowing effect.Results of the optical properties measurements disclosed that the transmittance of the film was in the region of 70%-88% and the optical properties of the film grown for 40 min were better than those grown under other conditions.The energy band gap of the film deposited with 40 min was around 3.63 eV.

  13. Estimating evolution of δ13CH4 during methanization of cellulosic waste based on stoichiometric chemical reactions, microbial dynamics and stable carbon isotope fractionation.

    Science.gov (United States)

    Vavilin, V A

    2012-04-01

    A change in δ(13)CH(4) during mesophilic methanization of cellulosic waste (paper and cardboard) was described using a mathematical model based on stoichiometric chemical reactions, microbial dynamics and the equation for the (13)C isotope accumulation in products including isotope fractionation. In this study, experimental data, previously obtained by Qu et al. (2009), was used to model metabolic pathways of cellulose transformation. A significant change in δ(13)CH(4) occurred in time during cellulosic waste methanization which was in accordance with the model. It was explained by the change in input of acetoclastic and hydrogenotrophic methanogenesis as well as by fractionation of stable carbon isotopes (13)C and (12)C which was much higher for hydrogenotrophic methanogenesis when compared to acetoclastic methanogenesis.

  14. Fluid dynamics, particulate segregation, chemical processes, and natural ore analog discussions that relate to the potential for criticality in Hanford tanks

    Energy Technology Data Exchange (ETDEWEB)

    Barney, G.S.

    1996-09-27

    This report presents an in-depth review of the potential for nuclear criticality to occur in Hanford defense waste tanks during past, current and future safe storage and maintenance operations. The report also briefly discusses the potential impacts of proposed retrieval activities, although retrieval was not a main focus of scope. After thorough review of fluid dynamic aspects that focus on particle segregation, chemical aspects that focus on solubility and adsorption processes that might concentrate plutonium and/or separate plutonium from the neutron absorbers in the tank waste, and ore-body formation and mining operations, the interdisciplinary team has come to the conclusion that there is negligible risk of nuclear critically under existing storage conditions in Hanford site underground waste storage tanks. Further, for the accident scenarios considered an accidental criticality is incredible.

  15. Achieved blood pressure and cardiovascular outcomes in high-risk patients: results from ONTARGET and TRANSCEND trials.

    Science.gov (United States)

    Böhm, Michael; Schumacher, Helmut; Teo, Koon K; Lonn, Eva M; Mahfoud, Felix; Mann, Johannes F E; Mancia, Giuseppe; Redon, Josep; Schmieder, Roland E; Sliwa, Karen; Weber, Michael A; Williams, Bryan; Yusuf, Salim

    2017-06-03

    Studies have challenged the appropriateness of accepted blood pressure targets. We hypothesised that different levels of low blood pressure are associated with benefit for some, but harm for other outcomes. In this analysis, we assessed the previously reported outcome data from high-risk patients aged 55 years or older with a history of cardiovascular disease, 70% of whom had hypertension, from the ONTARGET and TRANSCEND trials investigating ramipril, telmisartan, and their combination, with a median follow-up of 56 months. Detailed descriptions of randomisation and intervention have already been reported. We analysed the associations between mean blood pressure achieved on treatment; prerandomisation baseline blood pressure; or time-updated blood pressure (last on treatment value before an event) on the composite outcome of cardiovascular death, myocardial infarction, stroke, and hospital admission for heart failure; the components of the composite outcome; and all-cause death. Analysis was done by Cox regression analysis, ANOVA, and χ(2). These trials were registered with ClinicalTrials.gov, number NCT00153101. Recruitment for ONTARGET took place between Dec 1, 2001, and July 31, 2008. TRANSCEND took place between Nov 1, 2001, and May 30, 2004. 30 937 patients were recruited from 733 centres in 40 countries and followed up for a median of 56 months. In ONTARGET, 25 127 patients known to be tolerant to angiotensin-converting-enzyme (ACE)-inhibitors were randomly assigned after a run-in period to oral ramipril 10 mg/day (n=8407), telmisartan 80 mg/day (n=8386), or the combination of both (n=8334). In TRANSCEND, 5810 patients who were intolerant to ACE-inhibitors were randomly assigned to oral telmisartan 80 mg/day (n=2903) or placebo (n=2907). Baseline systolic blood pressure (SBP) 140 mm Hg or higher was associated with greater incidence of all outcomes compared with 120 mm Hg to less than 140 mm Hg. By contrast, a baseline diastolic blood pressure (DBP) less

  16. Exploring the dynamics of reaction N((2)D)+C2H4 with crossed molecular-beam experiments and quantum-chemical calculations.

    Science.gov (United States)

    Lee, Shih-Huang; Chin, Chih-Hao; Chen, Wei-Kan; Huang, Wen-Jian; Hsieh, Chu-Chun

    2011-05-14

    We conducted the title reaction using a crossed molecular-beam apparatus, quantum-chemical calculations, and RRKM calculations. Synchrotron radiation from an undulator served to ionize selectively reaction products by advantage of negligibly small dissociative ionization. We observed two products with gross formula C(2)H(3)N and C(2)H(2)N associated with loss of one and two hydrogen atoms, respectively. Measurements of kinetic-energy distributions, angular distributions, low-resolution photoionization spectra, and branching ratios of the two products were carried out. Furthermore, we evaluated total branching ratios of various exit channels using RRKM calculations based on the potential-energy surface of reaction N((2)D)+C(2)H(4) established with the method CCSD(T)/6-311+G(3df,2p)//B3LYP/6-311G(d,p)+ZPE[B3LYP/6-311G(d,p)]. The combination of experimental and computational results allows us to reveal the reaction dynamics. The N((2)D) atom adds to the C=C π-bond of ethene (C(2)H(4)) to form a cyclic complex c-CH(2)(N)CH(2) that directly ejects a hydrogen atom or rearranges to other intermediates followed by elimination of a hydrogen atom to produce C(2)H(3)N; c-CH(2)(N)CH+H is the dominant product channel. Subsequently, most C(2)H(3)N radicals, notably c-CH(2)(N)CH, further decompose to CH(2)CN+H. This work provides results and explanations different from the previous work of Balucani et al. [J. Phys. Chem. A, 2000, 104, 5655], indicating that selective photoionization with synchrotron radiation as an ionization source is a good choice in chemical dynamics research.

  17. Molecular Dynamics Simulations of Chemically Disordered Ferroelectric (Ba,Sr)TiO3 with a Semi-Empirical Effective Hamiltonian

    Science.gov (United States)

    Nishimatsu, Takeshi; Grünebohm, Anna; Waghmare, Umesh V.; Kubo, Momoji

    2016-11-01

    We present a semi-empirical effective Hamiltonian to capture effects of disorder associated with Ba and Sr cations occupying A sites in (BaxSr1-x)TiO3 on its ferroelectric phase transition. Averaging between the parameters of first-principles effective Hamiltonians of end members BaTiO3 and SrTiO3, we include a term with an empirical parameter to capture the local polarization and strains arising from the difference between ionic radii of Ba and Sr. Using mixed-space molecular dynamics of the effective Hamiltonian, we determine T-dependent ferroelectric phase transitions in (BaxSr1-x)TiO3 which are in good agreement with experiment. Our scheme of determination of semi-empirical parameters in effective Hamiltonian should be applicable to other perovskite-type ferroelectric solid solutions.

  18. Chemically-specific time-resolved surface photovoltage spectroscopy: Carrier dynamics at the interface of quantum dots attached to a metal oxide

    Science.gov (United States)

    Spencer, Ben F.; Cliffe, Matthew J.; Graham, Darren M.; Hardman, Samantha J. O.; Seddon, Elaine A.; Syres, Karen L.; Thomas, Andrew G.; Sirotti, Fausto; Silly, Mathieu G.; Akhtar, Javeed; O'Brien, Paul; Fairclough, Simon M.; Smith, Jason M.; Chattopadhyay, Swapan; Flavell, Wendy R.

    2015-11-01

    We describe a new experimental pump-probe methodology where a 2D delay-line detector enables fast (ns) monitoring of a narrow XPS spectrum in combination with a continuous pump laser. This has been developed at the TEMPO beamline at Synchrotron SOLEIL to enable the study of systems with intrinsically slow electron dynamics, and to complement faster measurements that use a fs laser as the pump. We demonstrate its use in a time-resolved study of the surface photovoltage of the m-plane ZnO (10 1 bar 0) surface which shows persistent photoconductivity, requiring monitoring periods on ms timescales and longer. We make measurements from this surface in the presence and absence of chemically-linked quantum dots (QDs), using type I PbS and type II CdSe/ZnSe (core/shell) QDs as examples. We monitor signals from both the ZnO substrate and the bound QDs during photoexcitation, yielding evidence for charge injection from the QDs into the ZnO. The chemical specificity of the technique allows us to observe differences in the extent to which the QD systems are influenced by the field of the surface depletion layer at the ZnO surface, which we attribute to differences in the band structure at the interface.

  19. Novel serine-based gemini surfactants as chemical permeation enhancers of local anesthetics: A comprehensive study on structure-activity relationships, molecular dynamics and dermal delivery.

    Science.gov (United States)

    Teixeira, Raquel S; Cova, Tânia F G G; Silva, Sérgio M C; Oliveira, Rita; do Vale, M Luísa C; Marques, Eduardo F; Pais, Alberto A C C; Veiga, Francisco J B

    2015-06-01

    This work aims at studying the efficacy of a series of novel biocompatible, serine-based surfactants as chemical permeation enhancers for two different local anesthetics, tetracaine and ropivacaine, combining an experimental and computational approach. The surfactants consist of gemini molecules structurally related, but with variations in headgroup charge (nonionic vs. cationic) and in the hydrocarbon chain lengths (main and spacer chains). In vitro permeation and molecular dynamics studies combined with cytotoxicity profiles were performed to investigate the permeation of both drugs, probe skin integrity, and rationalize the interactions at molecular level. Results show that these enhancers do not have significant deleterious effects on the skin structure and do not cause relevant changes on cell viability. Permeation across the skin is clearly improved using some of the selected serine-based gemini surfactants, namely the cationic ones with long alkyl chains and shorter spacer. This is noteworthy in the case of ropivacaine hydrochloride, which is not easily administered through the stratum corneum. Molecular dynamics results provide a mechanistic view of the surfactant action on lipid membranes that essentially corroborate the experimental observations. Overall, this study suggests the viability of these serine-based surfactants as suitable and promising delivery agents in pharmaceutical formulations.

  20. Advances in chemical physics

    CERN Document Server

    Rice, Stuart A

    2012-01-01

    The Advances in Chemical Physics series-the cutting edge of research in chemical physics The Advances in Chemical Physics series provides the chemical physics field with a forum for critical, authoritative evaluations of advances in every area of the discipline. Filled with cutting-edge research reported in a cohesive manner not found elsewhere in the literature, each volume of the Advances in Chemical Physics series serves as the perfect supplement to any advanced graduate class devoted to the study of chemical physics. This volume explores: Quantum Dynamical Resonances in Ch

  1. Insights from the Outskirts: Chemical and Dynamical Properties in the outer Parts of the Fornax Dwarf Spheroidal Galaxy

    CERN Document Server

    Hendricks, Benjamin; Walker, Matthew; Johnson, Christian I; Penarrubia, Jorge; Gilmore, Gerard

    2014-01-01

    We present radial velocities and [Fe/H] abundances for 340 stars in the Fornax dwarf spheroidal from R~16,000 spectra. The targets have been obtained in the outer parts of the galaxy, a region which has been poorly studied before. Our sample shows a wide range in [Fe/H], between -0.5 and -3.0 dex, in which we detect three subgroups. Removal of stars belonging to the most metal-rich population produces a truncated metallicity distribution function that is identical to Sculptor, indicating that these systems have shared a similar early evolution, only that Fornax experienced a late, intense period of star formation (SF). The derived age-metallicity relation shows a fast increase in [Fe/H] at early ages, after which the enrichment flattens significantly for stars younger than ~8 Gyr. Additionally, the data indicate a strong population of stars around 4 Gyr, followed by a second rapid enrichment in [Fe/H]. A leaky-box chemical enrichment model generally matches the observed relation but does not predict a signifi...

  2. Non-Covalent Interactions and Internal Dynamics in Pyridine-Ammonia a Combined Quantum-Chemical and Microwave Spectroscopy Study

    Science.gov (United States)

    Spada, Lorenzo; Tasinato, Nicola; Vazart, Fanny; Barone, Vincenzo; Caminati, Walther; Puzzarini, Cristina

    2017-06-01

    The 1:1 complex of ammonia with pyridine has been characterized by using state-of-the-art quantum-chemical computations combined with pulsed-jet Fourier-Transform microwave spectroscopy. The computed potential energy landscape pointed out the formation of a stable σ-type complex, which has been confirmed experimentally: the analysis of the rotational spectrum showed the presence of only one 1:1 pyridine - ammonia adduct. Each rotational transition is split into several components due to the internal rotation of NH_3 around its C_3 axis and to the hyperfine structure of both ^{14}N quadrupolar nuclei, thus providing the unequivocal proof that the two molecules form a σ-type complex involving both a N-H\\cdotsN and a C-H\\cdotsN hydrogen bond. The dissociation energy (BSSE and ZPE corrected) has been estimated to be 11.5 kJ\\cdotmol^{-1}. This work represents the first application of an accurate, yet efficient computational scheme, designed for the investigation of small biomolecules, to a molecular cluster.

  3. Effects of chemical composition and test conditions on the dynamic tensile response of Zr-based metallic glasses

    Science.gov (United States)

    Wang, F.; Laws, K.; Martinez, D.; Trujillo, C. P.; Brown, A. D.; Cerreta, E. K.; Hazell, P. J.; Ferry, M.; Quadir, M. Z.; Jiang, J.; Escobedo, J. P.

    2017-01-01

    The effects of impact velocity and temperature on the dynamic mechanical behavior of two bulk metallic (BMG) alloys with slightly different elemental compositions (Zr55Cu30Ni5Al30 and Zr46Cu38Ag8Al38) have been investigated. Bullet-shaped samples were accelerated by a gas gun to speeds in the 400˜600m/s range and tested at both room temperature and 250°C. The samples impacted steel extrusion dies which subjected the bullets to high strains at relatively high strain-rates. The extruded fragments were subsequently soft recovered by using low density foams and examined by means of optical/scanning electron microscopy and differential scanning calorimetry. It was found that shear banding was the dictating mechanism responsible for the fracture of all BMGs. At room temperature, the Zr55Cu30Ni5Al30 alloy exhibited a higher resistance to fragmentation than the Zr46Cu38Ag8Al38 alloy. At 250°C, significant melting was observed in the recovered fragments of both alloys, which indicates that the BMG glassy structure undergoes a melting process and deformation likely occurs homogeneously.

  4. Quantum chemical molecular dynamics simulation of single-walled carbon nanotube cap nucleation on an iron particle.

    Science.gov (United States)

    Ohta, Yasuhito; Okamoto, Yoshiko; Page, Alister J; Irle, Stephan; Morokuma, Keiji

    2009-11-24

    The atomic scale details of single-walled carbon nanotube (SWNT) nucleation on metal catalyst particles are elusive to experimental observations. Computer simulation of metal-catalyzed SWNT nucleation is a challenging topic but potentially of great importance to understand the factors affecting SWNT diameters, chirality, and growth efficiency. In this work, we use nonequilibrium density functional tight-binding molecular dynamics simulations and report nucleation of sp(2)-carbon cap structures on an iron particle consisting of 38 atoms. One C(2) molecule was placed every 1.0 ps around an Fe(38) cluster for 30 ps, after which a further 410 ps of annealing simulation without carbon supply was performed. We find that sp(2)-carbon network nucleation and annealing processes occur in three sequential and repetitive stages: (A) polyyne chains on the metal surface react with each other to evolve into a Y-shaped polyyne junction, which preferentially form a five-membered ring as a nucleus; (B) polyyne chains on the first five-membered ring form an additional fused five- or six-membered ring; and (C) pentagon-to-hexagon self-healing rearrangement takes place with the help of short-lived polyyne chains, stabilized by the mobile metal atoms. The observed nucleation process resembles the formation of a fullerene cage. However, the metal particle plays a key role in differentiating the nucleation process from fullerene cage formation, most importantly by keeping the growing cap structure from closing into a fullerene cage and by keeping the carbon edge "alive" for the addition of new carbon material.

  5. Self-Awareness, Self-Regulation, and Self-Transcendence (S-ART: A Framework for Understanding the Neurobiological Mechanisms of Mindfulness

    Directory of Open Access Journals (Sweden)

    David R. Vago

    2012-10-01

    Full Text Available Mindfulness - as a state, trait, process, type of meditation, and intervention has proven to be beneficial across a diverse group of psychological disorders as well as for general stress reduction. Yet, there remains a lack of clarity in the operationalization of this construct, and underlying mechanisms. Here, we provide an integrative theoretical framework and systems-based neurobiological model that explains the mechanisms by which mindfulness reduces biases related to self-processing and creates a sustainable healthy mind. Mindfulness is described through systematic mental training that develops meta-awareness (self-awareness, an ability to effectively modulate one’s behavior (self-regulation, and the development of a positive relationship between self and other that transcends self-focused needs and increases prosocial characteristics (self-transcendence. This framework of self-awareness, regulation, and transcendence (S-ART illustrates a method for becoming aware of the conditions that cause (and remove distortions or biases. The development of S-ART through meditation is proposed to modulate self-specifying and narrative self-networks through an integrative fronto-parietal control network. Relevant perceptual, cognitive, emotional, and behavioral neuropsychological processes are highlighted, including intention and motivation, attention regulation, emotion regulation, extinction and reconsolidation, prosociality, non-attachment and decentering. The S-ART framework and neurobiological model is based on our growing understanding of the mechanisms for neurocognition, empirical literature, and through dismantling the specific meditation practices thought to cultivate mindfulness. The proposed framework will inform future research in the contemplative sciences and target specific areas for development in the treatment of psychological disorders.

  6. Self-awareness, self-regulation, and self-transcendence (S-ART): a framework for understanding the neurobiological mechanisms of mindfulness.

    Science.gov (United States)

    Vago, David R; Silbersweig, David A

    2012-01-01

    Mindfulness-as a state, trait, process, type of meditation, and intervention has proven to be beneficial across a diverse group of psychological disorders as well as for general stress reduction. Yet, there remains a lack of clarity in the operationalization of this construct, and underlying mechanisms. Here, we provide an integrative theoretical framework and systems-based neurobiological model that explains the mechanisms by which mindfulness reduces biases related to self-processing and creates a sustainable healthy mind. Mindfulness is described through systematic mental training that develops meta-awareness (self-awareness), an ability to effectively modulate one's behavior (self-regulation), and a positive relationship between self and other that transcends self-focused needs and increases prosocial characteristics (self-transcendence). This framework of self-awareness, -regulation, and -transcendence (S-ART) illustrates a method for becoming aware of the conditions that cause (and remove) distortions or biases. The development of S-ART through meditation is proposed to modulate self-specifying and narrative self-networks through an integrative fronto-parietal control network. Relevant perceptual, cognitive, emotional, and behavioral neuropsychological processes are highlighted as supporting mechanisms for S-ART, including intention and motivation, attention regulation, emotion regulation, extinction and reconsolidation, prosociality, non-attachment, and decentering. The S-ART framework and neurobiological model is based on our growing understanding of the mechanisms for neurocognition, empirical literature, and through dismantling the specific meditation practices thought to cultivate mindfulness. The proposed framework will inform future research in the contemplative sciences and target specific areas for development in the treatment of psychological disorders.

  7. Transcending the nation state

    DEFF Research Database (Denmark)

    Cort, Pia

    2009-01-01

    Throughout Europe, vocational education and training is undergoing reform and modernisation as part of a common EU policy process, the Copenhagen Process. The aim of this Process is initiate a pan-European modernisation of vocational education and training in order to meet the challenges of globa...

  8. Transcending Cognitive Individualism

    Science.gov (United States)

    Zerubavel, Eviatar; Smith, Eliot R.

    2010-01-01

    Advancing knowledge in many areas of psychology and neuroscience, underlined by dazzling images of brain scans, appear to many professionals and to the public to show that people are on the way to explaining cognition purely in terms of processes within the individual's head. Yet while such cognitive individualism still dominates the popular…

  9. Cien años de soledad, de Gabriel García Márquez. La solitude ontologique d'un monde sans transcendance.

    OpenAIRE

    Gladieu, Marie-Madeleine

    2010-01-01

    Gabriel García Márquez dans son roman Cent ans de solitude présente toute une lignée de personnages qui déambulent au fil de l'histoire pouvant laisser croire dans une premier temps en une apparente chaîne de solidarité qui se délite sous le poids de la mémoire et des événements historiques et ne laissant aucune transcendance qui pourrait apporter une consolation à la solitude absolue de Macondo.

  10. Cien años de soledad, de Gabriel García Márquez. La solitude ontologique d'un monde sans transcendance.

    OpenAIRE

    Gladieu, Marie-Madeleine

    2010-01-01

    Gabriel García Márquez dans son roman Cent ans de solitude présente toute une lignée de personnages qui déambulent au fil de l'histoire pouvant laisser croire dans une premier temps en une apparente chaîne de solidarité qui se délite sous le poids de la mémoire et des événements historiques et ne laissant aucune transcendance qui pourrait apporter une consolation à la solitude absolue de Macondo.

  11. Qualitative Aspects of the Solutions of a Mathematical Model for the Dynamic Analysis of the Reversible Chemical Reaction SO2(g)+1/2O2(g)<=>SO3(g) in a Catalytic Reactor

    CERN Document Server

    Wilfredo, Angulo

    2014-01-01

    We present some qualitative aspects concerning the solution to the mathematical model describing the dynamical behavior of the reversible chemical reaction SO2(g)+1/2O2(g)SO3(g) carried out in a catalytic reactor used in the process of sulfuric acid production.

  12. Qualitative Aspects of the Solutions of a Mathematical Model for the Dynamic Analysis of the Reversible Chemical Reaction SO2(g)+1/2O2(g)<=>SO3(g) in a Catalytic Reactor

    OpenAIRE

    Wilfredo, Angulo; Joyne, Contreras

    2014-01-01

    We present some qualitative aspects concerning the solution to the mathematical model describing the dynamical behavior of the reversible chemical reaction SO2(g)+1/2O2(g)SO3(g) carried out in a catalytic reactor used in the process of sulfuric acid production.

  13. Short-term temporal variation in sporulation dynamics of arbuscular mycorrhizal (AM) fungi and physico-chemical edaphic properties of wheat rhizosphere.

    Science.gov (United States)

    Panwar, Vipin; Meghvansi, M K; Siddiqui, Sazada

    2011-07-01

    In this study, we investigated the pattern of short-term temporal variation in the arbuscular mycorrhizal (AM) fungi and physico-chemical edaphic properties of some wheat growing areas of the Bundelkhand region, Central India. Rhizospheric soil samples were collected every month from December 2007 to May 2008 from four wheat growing sites around Jhansi (Bundelkhand region). AM fungal root colonization, sporulation and physico-chemical edaphic properties during this period were determined and compared to evaluate the dynamics of response of wheat towards the AMF along crop maturation. Maximum AMF root colonization recorded was 54.3% indicating that AMF, particularly in low phosphorus (P) soils, can be important even in case of less responsive crop like wheat. In the two out of four sites studied, the AMF spore density increased with the increase in soil temperature. Absence of this type of pattern in remaining two sites indicated that site-specific environmental and agricultural conditions may affect the degree of wheat response to AMF. It also suggested that AMF communities inhabiting agroecosystems may exhibit considerable temporal sporulation patterns. The maximum AMF colonization was observed during February-March 2008, whereas maximum AMF sporulation was noticed during March-April 2008. Statistically significant negative correlation of AMF spore density with pH, organic carbon (OC) and available P was observed in the one of the sites studied. Overall assessment of the data indicated that season and location significantly affected the interaction of AM fungi with winter wheat necessitating the further need to understand the ecology of AMF populations with reference to specific host species under different micro-climatic conditions of Bundelkhand region.

  14. Level crossing analysis of chemically induced dynamic nuclear polarization: Towards a common description of liquid-state and solid-state cases

    Science.gov (United States)

    Sosnovsky, Denis V.; Jeschke, Gunnar; Matysik, Jörg; Vieth, Hans-Martin; Ivanov, Konstantin L.

    2016-04-01

    Chemically Induced Dynamic Nuclear Polarization (CIDNP) is an efficient method of creating non-equilibrium polarization of nuclear spins by using chemical reactions, which have radical pairs as intermediates. The CIDNP effect originates from (i) electron spin-selective recombination of radical pairs and (ii) the dependence of the inter-system crossing rate in radical pairs on the state of magnetic nuclei. The CIDNP effect can be investigated by using Nuclear Magnetic Resonance (NMR) methods. The gain from CIDNP is then two-fold: it allows one to obtain considerable amplification of NMR signals; in addition, it provides a very useful tool for investigating elusive radicals and radical pairs. While the mechanisms of the CIDNP effect in liquids are well established and understood, detailed analysis of solid-state CIDNP mechanisms still remains challenging; likewise a common theoretical frame for the description of CIDNP in both solids and liquids is missing. Difficulties in understanding the spin dynamics that lead to the CIDNP effect in the solid-state case are caused by the anisotropy of spin interactions, which increase the complexity of spin evolution. In this work, we propose to analyze CIDNP in terms of level crossing phenomena, namely, to attribute features in the CIDNP magnetic field dependence to Level Crossings (LCs) and Level Anti-Crossings (LACs) in a radical pair. This approach allows one to describe liquid-state CIDNP; the same holds for the solid-state case where anisotropic interactions play a significant role in CIDNP formation. In solids, features arise predominantly from LACs, since in most cases anisotropic couplings result in perturbations, which turn LCs into LACs. We have interpreted the CIDNP mechanisms in terms of the LC/LAC concept. This consideration allows one to find analytical expressions for a wide magnetic field range, where several different mechanisms are operative; furthermore, the LAC description gives a way to determine CIDNP sign

  15. Level crossing analysis of chemically induced dynamic nuclear polarization: Towards a common description of liquid-state and solid-state cases.

    Science.gov (United States)

    Sosnovsky, Denis V; Jeschke, Gunnar; Matysik, Jörg; Vieth, Hans-Martin; Ivanov, Konstantin L

    2016-04-14

    Chemically Induced Dynamic Nuclear Polarization (CIDNP) is an efficient method of creating non-equilibrium polarization of nuclear spins by using chemical reactions, which have radical pairs as intermediates. The CIDNP effect originates from (i) electron spin-selective recombination of radical pairs and (ii) the dependence of the inter-system crossing rate in radical pairs on the state of magnetic nuclei. The CIDNP effect can be investigated by using Nuclear Magnetic Resonance (NMR) methods. The gain from CIDNP is then two-fold: it allows one to obtain considerable amplification of NMR signals; in addition, it provides a very useful tool for investigating elusive radicals and radical pairs. While the mechanisms of the CIDNP effect in liquids are well established and understood, detailed analysis of solid-state CIDNP mechanisms still remains challenging; likewise a common theoretical frame for the description of CIDNP in both solids and liquids is missing. Difficulties in understanding the spin dynamics that lead to the CIDNP effect in the solid-state case are caused by the anisotropy of spin interactions, which increase the complexity of spin evolution. In this work, we propose to analyze CIDNP in terms of level crossing phenomena, namely, to attribute features in the CIDNP magnetic field dependence to Level Crossings (LCs) and Level Anti-Crossings (LACs) in a radical pair. This approach allows one to describe liquid-state CIDNP; the same holds for the solid-state case where anisotropic interactions play a significant role in CIDNP formation. In solids, features arise predominantly from LACs, since in most cases anisotropic couplings result in perturbations, which turn LCs into LACs. We have interpreted the CIDNP mechanisms in terms of the LC/LAC concept. This consideration allows one to find analytical expressions for a wide magnetic field range, where several different mechanisms are operative; furthermore, the LAC description gives a way to determine CIDNP sign

  16. Coupling the chemical dynamics of carbonate and dissolved inorganic nitrogen systems in the eutrophic and turbid inner Changjiang (Yangtze River) Estuary

    Science.gov (United States)

    Zhai, W.-D.; Yan, X.-L.

    2015-04-01

    To better understand biogeochemical processes controlling CO2 dynamics in those eutrophic large-river estuaries and coastal lagoons, we investigated surface water carbonate system, nutrients, and relevant hydrochemical parameters in the inner Changjiang (Yangtze River) Estuary, covering its channel-like South Branch and the lagoon-like North Branch, shortly after a spring-tide period in April 2010. In the North Branch, with a water residence time of more than 2 months, biogeochemical additions of ammonium (7.4 to 65.7 μmol kg-1) and alkalinity (196 to 695 μmol kg-1) were detected along with high salinity of 4.5 to 17.4. In the South Branch upper-reach, unusual salinity values of 0.20 to 0.67 were detected, indicating spillover waters from the North Branch. The spillover waters enhanced the springtime Changjiang export fluxes of nutrients, dissolved inorganic carbon, and alkalinity. And they affected the biogeochemistry in the South Branch, by lowering water-to-air CO2 flux and continuing the nitrification reaction. In the North Branch, pCO2 was measured from 930 to 1518 μatm at the salinity range between 8 and 16, which was substantially higher than the South Branch pCO2 of 700 to 1100 μatm. Based on field data analyses and simplified stoichiometric equations, we suggest that the North Branch CO2 productions were quantified by biogeochemical processes combining organic matter decomposition, nitrification, CaCO3 dissolution, and acid-base reactions in the estuarine mixing zone. Although our study is subject to limited temporal and spatial coverage of sampling, we have demonstrated a procedure to quantificationally constrain net CO2 productions in eutrophic estuaries and/or coastal lagoons, by coupling the chemical dynamics of carbonate and dissolved inorganic nitrogen systems.

  17. Prediction of fried pine nuts shelf life by chemical dynamics method%化学动力学法预测炒制松籽的货架期

    Institute of Scientific and Technical Information of China (English)

    刘志明; 于金池; 冯玉超; 何宇; 赵婉舒

    2015-01-01

    The oxidizing deterioration degree of fried pine nuts oil was estimated by peroxide value(POV)in its storage process, and the fried pine nuts shelf life (SL)was predicted with chemical kinetics method. Determined the POV changes of fried pine nuts as time under the storage conditions of 25℃ and 40℃storage temperature,5.3 kPa, 10.5 kPa and 21.0 kPa oxygen partial pressure, return chemical kinetics equation, calculated reaction rate constant (k) and activa-tion energy (Ea),then combined with POV limit that fried pine nuts was inedible to build chemical kinetics model to predict SL of fried pine nuts. The results show that fried pine nuts oil oxidation belongs to first order kinetics reaction, the conformity of SL predicted values and sensory evaluation results was 75%to 96%. SL prediction of fried pine nuts has strong regularity and practicability by POV parameters and dynamic method. The study show that SL of fried pine nuts can be prolonged under condition of low oxygen atmosphere and low storage temperature.%以过氧化值(POV)衡量炒制松籽油脂在贮存过程中发生氧化劣变的程度,用化学动力学方法预测炒制松籽货架期(SL).测定炒制松籽在25℃和40℃2个贮藏温度,5.3 kPa、10.5 kPa和21.0 kPa3种氧气分压的贮藏条件下POV随时间的变化情况,回归化学动力学方程,求算反应速率常数(k)和活化能(Ea),结合感官评定确定炒制松籽不能食用时的POV限值,建立化学动力学模型,预测炒制松籽的SL.结果表明,炒制松籽油脂氧化属于一级动力学反应, SL预测值与感官评定结果符合度在75%~96%.用POV参数,以动力学方法预测炒制松籽SL具有较强的规律性和实用性.研究表明,在缺氧氛围和低温条件下贮存可延长炒制松籽的SL.

  18. "Structure and dynamics in complex chemical systems: Gaining new insights through recent advances in time-resolved spectroscopies.” ACS Division of Physical Chemistry Symposium presented at the Fall National ACS Meeting in Boston, MA, August 2015

    Energy Technology Data Exchange (ETDEWEB)

    Crawford, Daniel [Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States)

    2016-09-26

    8-Session Symposium on STRUCTURE AND DYNAMICS IN COMPLEX CHEMICAL SYSTEMS: GAINING NEW INSIGHTS THROUGH RECENT ADVANCES IN TIME-RESOLVED SPECTROSCOPIES. The intricacy of most chemical, biochemical, and material processes and their applications are underscored by the complex nature of the environments in which they occur. Substantial challenges for building a global understanding of a heterogeneous system include (1) identifying unique signatures associated with specific structural motifs within the heterogeneous distribution, and (2) resolving the significance of each of multiple time scales involved in both small- and large-scale nuclear reorganization. This symposium focuses on the progress in our understanding of dynamics in complex systems driven by recent innovations in time-resolved spectroscopies and theoretical developments. Such advancement is critical for driving discovery at the molecular level facilitating new applications. Broad areas of interest include: Structural relaxation and the impact of structure on dynamics in liquids, interfaces, biochemical systems, materials, and other heterogeneous environments.

  19. Structure of N'-(adamantan-2-ylidene)benzohydrazide, a potential antibacterial agent, in solution: Molecular dynamics simulations, quantum chemical calculations and Ultraviolet–visible spectroscopy studies

    Indian Academy of Sciences (India)

    ALEXANDER M ANDRIANOV; IVAN A KASHYN; VIKTOR M ANDRIANOV; MAKSIM B SHUNDALAU; ANTON V HLINISTY; SERGEY V GAPONENKO; ELENA V SHABUNYA -KLYACHKOVSKAYA; ANNA MATSUKOVICH; ABDUL-MALEK S AL- TAMIMI; ALI A EL- EMAM

    2016-12-01

    The molecular dynamics simulations of the structure of the N'-(adamantan-2-ylidene)benzohydrazide followed by the quantum chemical calculations at the DFT level of theory have identified four stable conformers of this potential antibacterial agent in solution: one “central” cis- and three (“central”, “left” and “right”) trans-conformers. The UV-Vis absorption spectrum in the 220–320 nm region in the ethanol solution reveals two bands that can be primarily explained based on the ab initio calculations of the spectral characteristics of the “side” trans-conformers at the MRPT level of theory. However, the close energy values for thecalculated cis- S₁ ← S₀ and “side” trans- S₂ ← S₀ transitions cannot exclude the presence of cis-conformer in solution. Therefore, the data obtained show that the coexistence of both trans-conformers and cis-conformer should be taken into consideration when studying the pharmaceutical properties of the title molecule.

  20. Quantum chemical study on influence of intermolecular hydrogen bonding on the geometry, the atomic charges and the vibrational dynamics of 2,6-dichlorobenzonitrile.

    Science.gov (United States)

    Agarwal, Parag; Bee, Saba; Gupta, Archana; Tandon, Poonam; Rastogi, V K; Mishra, Soni; Rawat, Poonam

    2014-01-01

    FT-IR (4000-400 cm(-1)) and FT-Raman (4000-200 cm(-1)) spectral measurements on solid 2,6-dichlorobenzonitrile (2,6-DCBN) have been done. The molecular geometry, harmonic vibrational frequencies and bonding features in the ground state have been calculated by density functional theory at the B3LYP/6-311++G (d,p) level. A comparison between the calculated and the experimental results covering the molecular structure has been made. The assignments of the fundamental vibrational modes have been done on the basis of the potential energy distribution (PED). To investigate the influence of intermolecular hydrogen bonding on the geometry, the charge distribution and the vibrational spectrum of 2,6-DCBN; calculations have been done for the monomer as well as the tetramer. The intermolecular interaction energies corrected for basis set superposition error (BSSE) have been calculated using counterpoise method. Based on these results, the correlations between the vibrational modes and the structure of the tetramer have been discussed. Molecular electrostatic potential (MEP) contour map has been plotted in order to predict how different geometries could interact. The Natural Bond Orbital (NBO) analysis has been done for the chemical interpretation of hyperconjugative interactions and electron density transfer between occupied (bonding or lone pair) orbitals to unoccupied (antibonding or Rydberg) orbitals. UV spectrum was measured in methanol solution. The energies and oscillator strengths were calculated by Time Dependent Density Functional Theory (TD-DFT) and matched to the experimental findings. TD-DFT method has also been used for theoretically studying the hydrogen bonding dynamics by monitoring the spectral shifts of some characteristic vibrational modes involved in the formation of hydrogen bonds in the ground and the first excited state. The (13)C nuclear magnetic resonance (NMR) chemical shifts of the molecule were calculated by the Gauge independent atomic orbital

  1. Chemical Emergencies

    Science.gov (United States)

    When a hazardous chemical has been released, it may harm people's health. Chemical releases can be unintentional, as in the case of an ... the case of a terrorist attack with a chemical weapon. Some hazardous chemicals have been developed by ...

  2. Dynamic processes and chemical composition of Lepidium sativum seeds determined by means of field-cycling NMR relaxometry and NMR spectroscopy.

    Science.gov (United States)

    Rachocki, A; Latanowicz, L; Tritt-Goc, J

    2012-12-01

    Proton nuclear magnetic resonance (NMR) techniques, such as field-cycling relaxometry, wide-line NMR spectroscopy, and magic angle spinning NMR spectroscopy, were applied to study the seeds of cress, Lepidium sativum. Field-cycling NMR relaxometry was used for the first time to investigate the properties of the whole molecular system of dry cress seeds. This method not only allowed the dynamics to be studied, but was also successful in the differentiation among the solid (i.e., carbohydrates, proteins, or fats forming a solid form of lipids) and liquid-like (oil compounds) components of the seeds. The (1)H NMR relaxation dispersion of oils was interpreted as a superposition of intramolecular and intermolecular contributions. The intramolecular part was described in terms of a Lorentzian spectral density function, whereas a log-Gaussian distribution of correlation times was applied for the intermolecular dipole-dipole contribution. The models applied led to very good agreement with the experimental data and demonstrate that the contribution of the intermolecular relaxation to the overall relaxation should not be disregarded, especially at low frequencies. A power-law frequency dependence of the proton relaxation dispersion was used for the interpretation of the solid components. From the analysis of the (1)H wide-line NMR spectra of the liquid-like component of hydrated cress seeds, we can conclude that the contribution of oil protons should always be taken into account when evaluating the spin-lattice relaxation times values or measuring the moisture and oil content. The application of (1)H magic angle spinning NMR significantly improves resolution in the liquid-like spectrum of seeds and allows the determination of the chemical composition of cress seeds.

  3. Sampling of Organic Solutes in Aqueous and Heterogeneous Environments Using Oscillating Excess Chemical Potentials in Grand Canonical-like Monte Carlo-Molecular Dynamics Simulations.

    Science.gov (United States)

    Lakkaraju, Sirish Kaushik; Raman, E Prabhu; Yu, Wenbo; MacKerell, Alexander D

    2014-06-10

    Solute sampling of explicit bulk-phase aqueous environments in grand canonical (GC) ensemble simulations suffer from poor convergence due to low insertion probabilities of the solutes. To address this, we developed an iterative procedure involving Grand Canonical-like Monte Carlo (GCMC) and molecular dynamics (MD) simulations. Each iteration involves GCMC of both the solutes and water followed by MD, with the excess chemical potential (μex) of both the solute and the water oscillated to attain their target concentrations in the simulation system. By periodically varying the μex of the water and solutes over the GCMC-MD iterations, solute exchange probabilities and the spatial distributions of the solutes improved. The utility of the oscillating-μex GCMC-MD method is indicated by its ability to approximate the hydration free energy (HFE) of the individual solutes in aqueous solution as well as in dilute aqueous mixtures of multiple solutes. For seven organic solutes: benzene, propane, acetaldehyde, methanol, formamide, acetate, and methylammonium, the average μex of the solutes and the water converged close to their respective HFEs in both 1 M standard state and dilute aqueous mixture systems. The oscillating-μex GCMC methodology is also able to drive solute sampling in proteins in aqueous environments as shown using the occluded binding pocket of the T4 lysozyme L99A mutant as a model system. The approach was shown to satisfactorily reproduce the free energy of binding of benzene as well as sample the functional group requirements of the occluded pocket consistent with the crystal structures of known ligands bound to the L99A mutant as well as their relative binding affinities.

  4. Heideggerian dynamics and the monadological role of the 'between': A crossing with quantum brain dynamics.

    Science.gov (United States)

    Globus, Gordon

    2015-12-01

    Heideggerian theory is retrieved as a dynamics, the "Godly event" of das Ereignis ("enowning"), which is unexpectedly compatible with a version of quantum brain dynamics. In both the "between" (das Zwischen) has the fundamental role of the dis-closure that is Existenz. Heidegger's harsh critique of technology and science does not apply to revolutionary quantum brain dynamics. The crossing between Heidegger and quantum brain dynamics, as well as one fundamental ontological difference, illuminates both. To our surprise this difference turns out, contra Heidegger, to be monadological. The monadological conception is applied to long-standing problematics of measurement in quantum physics and consciousness in philosophy. Heideggerian Existenz is affirmed as fundamentally non-computational but is reformulated as a dynamical process of monadological dis-closure that radically deconstructs transcendent world. Copyright © 2015. Published by Elsevier Ltd.

  5. « Mon pays, c’est mes enfants et mes petits-enfants » : exils et transcendance dans Le Bonheur a la queue glissante d’Abla Farhoud

    Directory of Open Access Journals (Sweden)

    Kelly Anne Maddox

    2010-05-01

    Full Text Available L’identitaire dans ce premier roman de Farhoud est inextricablement liée à l’exil, que ce soit l’exil physique, ou bien, l’exil intérieur. D’une part, l’exil physique se manifeste par la migration, d’abord lorsque le personnage principal, Dounia, quitte son village pour vivre dans celui de son mari, et ensuite lorsqu’elle émigre au Canada. D’autre part, l’exil intérieur provient de la subordination imposée par la culture patriarcale. Nous comptons examiner ces deux formes d’exil, ainsi que les conséquences qui en résultent, telles que la marginalisation, la dépossession linguistique, et le refoulement identitaire. Nous discuterons également des tentatives qu’entreprend Dounia de transcender sa marginalisation en établissant des relations interpersonnelles.

  6. Harnessing complex emergent metaphors for effective communication in palliative care: a multimodal perceptual analysis of hospice patients' reports of transcendence experiences.

    Science.gov (United States)

    Arnold, Bruce L; Lloyd, Linda S

    2014-05-01

    Terminally ill patients can have unexpected, enigmatic, and profound cognitive shifts that significantly alter their perception of themselves, thereby eliminating their fear of death and dying. However, there are no systematic studies into these remarkable yet ineffable transcendence experiences. They therefore remain easily overlooked or viewed as isolated anomalies and therefore excluded from quality-of-life patient considerations. We use a multimodal methodology for identifying the prevalence and thematic properties of complex emergent metaphors patients use to report these experiences. Although previous research has pioneered the importance of understanding conventional or primary metaphors at the end of life, our findings indicate the considerable potential of more complex metaphors for reducing barriers to effective communication in palliative care.

  7. Título da página electrónica: Transcend – A Peace and Development Organisation for Conflict Transformation by Peaceful Means

    Directory of Open Access Journals (Sweden)

    Mónica Rafael Simões

    2012-10-01

    Full Text Available Transcend é uma organização de mediação de conflitos que tem como objectivo colocar a experiência e o conhecimento ao serviço das práticas de transformação de conflitos, construção da paz e desenvolvimento. Fundada em 1993 por Johan Galtung – seu director e um dos pais fundadores dos estudos para a paz –, esta organização “virtual” baseia-se no trabalho e comunicação em rede e fundamenta-se em 4 pilares principais: educação/formação, disseminação, pesquisa e acção. A acção para a tentativa d...

  8. On transcending the impasse of respiratory motion correction applications in routine clinical imaging - a consideration of a fully automated data driven motion control framework.

    Science.gov (United States)

    Kesner, Adam L; Schleyer, Paul J; Büther, Florian; Walter, Martin A; Schäfers, Klaus P; Koo, Phillip J

    2014-12-01

    Positron emission tomography (PET) is increasingly used for the detection, characterization, and follow-up of tumors located in the thorax. However, patient respiratory motion presents a unique limitation that hinders the application of high-resolution PET technology for this type of imaging. Efforts to transcend this limitation have been underway for more than a decade, yet PET remains for practical considerations a modality vulnerable to motion-induced image degradation. Respiratory motion control is not employed in routine clinical operations. In this article, we take an opportunity to highlight some of the recent advancements in data-driven motion control strategies and how they may form an underpinning for what we are presenting as a fully automated data-driven motion control framework. This framework represents an alternative direction for future endeavors in motion control and can conceptually connect individual focused studies with a strategy for addressing big picture challenges and goals.

  9. Connection between quantum systems involving the fourth Painlevé transcendent and k-step rational extensions of the harmonic oscillator related to Hermite exceptional orthogonal polynomial

    Science.gov (United States)

    Marquette, Ian; Quesne, Christiane

    2016-05-01

    The purpose of this communication is to point out the connection between a 1D quantum Hamiltonian involving the fourth Painlevé transcendent PIV, obtained in the context of second-order supersymmetric quantum mechanics and third-order ladder operators, with a hierarchy of families of quantum systems called k-step rational extensions of the harmonic oscillator and related with multi-indexed Xm1,m2,…,mk Hermite exceptional orthogonal polynomials of type III. The connection between these exactly solvable models is established at the level of the equivalence of the Hamiltonians using rational solutions of the fourth Painlevé equation in terms of generalized Hermite and Okamoto polynomials. We also relate the different ladder operators obtained by various combinations of supersymmetric constructions involving Darboux-Crum and Krein-Adler supercharges, their zero modes and the corresponding energies. These results will demonstrate and clarify the relation observed for a particular case in previous papers.

  10. Effect of Self-transcendence on the Acceptance of Disability among Patients with Stroke%自我超越对脑卒中患者残障接受度的影响

    Institute of Scientific and Technical Information of China (English)

    张琳; 赵炜; 旷咏梅; 周海燕

    2016-01-01

    目的调查脑卒中患者自我超越和残障接受度现状,分析自我超越对残障接受度的影响。方法应用中文版自我超越量表、残障接受度量表对476名脑卒中患者进行问卷调查。结果患者残障接受度得分为139.45±34.67;自我超越与残障接受度及其各维度呈正相关(P<0.05);分层回归分析结果显示,年龄、文化程度、自我超越是脑卒中患者残障接受度的影响因素。结论脑卒中患者的自我超越和残障接受度不高,自我超越是其残障接受度的影响因素。%Objective To investigate the current status of self-transcendence and the acceptance of disability among patients with stroke, and to explore the effect self-transcendence on acceptance of disability.Methods In total, 476 patients with stroke were investigated by self-transcendence scale and acceptance of disability scale.Results The score of acceptance of disability was (139.45±34.67). The self-transcendence was positively correlated (P<0.05) with the dimensions of acceptance of disability. Hierarchical regression analysis showed that the ages, degree of education and self-transcendence were the influencing factors of acceptance of disability.Conclusion The levels of self-transcendence and acceptance of disability among patients with stroke were low, and the self-transcendence were the influencing factors of acceptance of disability.

  11. COOEE bitumen: chemical aging

    CERN Document Server

    Lemarchand, Claire A; Dyre, Jeppe C; Hansen, Jesper S

    2013-01-01

    We study chemical aging in "COOEE bitumen" using molecular dynamic simulations. The model bitumen is composed of four realistic molecule types: saturated hydrocarbon, resinous oil, resin, and asphaltene. The aging reaction is modelled by the chemical reaction: "2 resins $\\rightarrow$ 1 asphaltene". Molecular dynamic simulations of four bitumen compositions, obtained by a repeated application of the aging reaction, are performed. The stress autocorrelation function, the fluid structure, the rotational dynamics of the plane aromatic molecules, and the diffusivity of each molecule, are determined for the four different compositions. The aging reaction causes a significant dynamics slowdown, which is correlated to the aggregation of asphaltene molecules in larger and dynamically slower nanoaggregates. Finally, a detailed description of the role of each molecule types in the aggregation and aging processes is given.

  12. Microscopic Models for Chemical Thermodynamics

    OpenAIRE

    Malyshev, Vadim A.

    2011-01-01

    We introduce an infinite particle system dynamics, which includes stochastic chemical kinetics models, the classical Kac model and free space movement. We study energy redistribution between two energy types (kinetic and chemical) in different time scales, similar to energy redistribution in the living organisms. One example is considered in great detail, where the model provides main formulas of chemical thermodynamics.

  13. Microscopic Models for Chemical Thermodynamics

    CERN Document Server

    Malyshev, V A

    2011-01-01

    We introduce an infinite particle system dynamics, which includes stochastic chemical kinetics models, the classical Kac model and free space movement. We study energy redistribution between two energy types (kinetic and chemical) in different time scales, similar to energy redistribution in the living cell. One example is considered in great detail, where the model provides main formulas of chemical thermodynamics.

  14. Microscopic Models for Chemical Thermodynamics

    Science.gov (United States)

    Malyshev, V. A.

    2005-06-01

    We introduce an infinite particle system dynamics, which includes stochastic chemical kinetics models, the classical Kac model and free space movement. We study energy redistribution between two energy types (kinetic and chemical) in different time scales, similar to energy redistribution in the living cell. One example is considered in great detail, where the model provides main formulas of chemical thermodynamics.

  15. 基于反馈神经网络的动态化工过程建模%Modeling Nonlinear Dynamic Chemical Process Base on Artificial Neural Networks

    Institute of Scientific and Technical Information of China (English)

    吴建锋; 何小荣; 等

    2001-01-01

    A new recurrent neural network, based on dynamic characteristics of chemical process, is put forward in this article. The structures of state feedback, time-delayed nodes and the integrated nodes are well combined in its structure so as to make the network memorize more past system states and keeping it from being too complex.The static BP algorithm is successfully used to train it. The new recurrent neural network is used to build models for a single-input-single-output (SISO) system and a multi-input-single-output (MISO) system and then the models are compared with other models based on BP neural networks.The comparison result shows multi-layer feed forward neural networks. The result shows that models based on the new recurrent neural networks are more reliable and have high capability of antijamming.%针对非线性动态化工过程建模存在的问题,提出了一种新的反馈神经网络结构,并将状态反馈、时间序列延迟以及集中节点的概念结合起来,用于提高反馈神经网络的性能,同时又使得网络结构不至于太复杂。在用此网络结构建模的时候,成功地将BP算法用于网络模型的训练。文中将这种反馈神经网络结构分别对一个单输入单输出(SISO)的非线性动态系统和一个多输入单输出(SIMO)的连续全混釜(CSTR)模型进行建模,并将所得模型与基于静态BP神经网络所得的模型在模型输出精度和抗干扰性等方面进行了比较,证明了该反馈神经网络在动态过程建模中能够比静态BP模型更好地反映出动态过程的输入输出关系,并具有一定的抗干扰能力。

  16. Hydrologic connections and dynamics of water movement in the classical Karst (Kras) Aquifer: evidence from frequent chemical and stable isotope sampling

    Science.gov (United States)

    Doctor, Daniel H.

    2008-01-01

    A review of past research on the hydrogeology of the Classical Karst (Kras) region and new information obtained from a two- year study using environmental tracers are presented in this paper. The main problems addressed are 1) the sources of water to the Kras aquifer resurgence zone-including the famous Timavo springs-under changing flow regimes; 2) a quantification of the storage volumes of the karst massif corresponding to flow regimes defined by hydrograph recessions of the Timavo springs; and 3) changing dynamics between deep phreatic conduit flow and shallow phreatic and epiphreatic storage within the aquifer resurgence zone as determined through changes in chemical and isotopic composition at springs and wells. Particular focus was placed on addressing the long-standing question of the influence of the Soca River on the ground waters of the aquifer resurgence zone. The results indicate that the alluvial aquifer supplied by the sinking of the Soca River on the northwestern edge of the massif contributes approximately 75% of the mean annual outflow to the smaller springs of the aquifer resurgence zone, and as much as 53% to the mean annual outflow of the Timavo springs. As a whole, the Soca River is estimated to contribute 56% of the average outflow of the Kras aquifer resurgence. The proportions of Soca River water increase under drier conditions, and decrease under wetter conditions. Time series analysis of oxygen stable isotope records indicate that the transit time of Soca River water to the Timavo springs, Sardos spring, and well B-4 is on the order of 1-2 months, depending on hydrological conditions. The total baseflow storage of the Timavo springs is estimated to be 518 million m3, and represents 88.5% of the storage capacity estimated for all flow regimes of the springs. The ratio of baseflow storage volume to the average annual volume discharged at the Timavo springs is 0.54. The Reka River sinking in Slovenia supplies substantial allogenic recharge to

  17. Development of a dynamic headspace solid-phase microextraction procedure coupled to GC-qMSD for evaluation the chemical profile in alcoholic beverages

    Energy Technology Data Exchange (ETDEWEB)

    Rodrigues, F.; Caldeira, M. [Centro de Quimica da Madeira, Departamento de Quimica, Universidade da Madeira, Campus Universitario da Penteada, 9000-390 Funchal (Portugal); Camara, J.S. [Centro de Quimica da Madeira, Departamento de Quimica, Universidade da Madeira, Campus Universitario da Penteada, 9000-390 Funchal (Portugal)], E-mail: jsc@uma.pt

    2008-02-18

    In the present study, a simple and sensitive methodology based on dynamic headspace solid-phase microextraction (HS-SPME) followed by thermal desorption gas chromatography with quadrupole mass detection (GC-qMSD), was developed and optimized for the determination of volatile (VOCs) and semi-volatile (SVOCs) compounds from different alcoholic beverages: wine, beer and whisky. Key experimental factors influencing the equilibrium of the VOCs and SVOCs between the sample and the SPME fibre, as the type of fibre coating, extraction time and temperature, sample stirring and ionic strength, were optimized. The performance of five commercially available SPME fibres was evaluated and compared, namely polydimethylsiloxane (PDMS, 100 {mu}m); polyacrylate (PA, 85 {mu}m); polydimethylsiloxane/divinylbenzene (PDMS/DVB, 65 {mu}m); carboxen{sup TM}/polydimethylsiloxane (CAR/PDMS, 75 {mu}m) and the divinylbenzene/carboxen on polydimethylsiloxane (DVB/CAR/PDMS, 50/30 {mu}m) (StableFlex). An objective comparison among different alcoholic beverages has been established in terms of qualitative and semi-quantitative differences on volatile and semi-volatile compounds. These compounds belong to several chemical families, including higher alcohols, ethyl esters, fatty acids, higher alcohol acetates, isoamyl esters, carbonyl compounds, furanic compounds, terpenoids, C13-norisoprenoids and volatile phenols. The optimized extraction conditions and GC-qMSD, lead to the successful identification of 44 compounds in white wines, 64 in beers and 104 in whiskys. Some of these compounds were found in all of the examined beverage samples. The main components of the HS-SPME found in white wines were ethyl octanoate (46.9%), ethyl decanoate (30.3%), ethyl 9-decenoate (10.7%), ethyl hexanoate (3.1%), and isoamyl octanoate (2.7%). As for beers, the major compounds were isoamyl alcohol (11.5%), ethyl octanoate (9.1%), isoamyl acetate (8.2%), 2-ethyl-1-hexanol (5.9%), and octanoic acid (5.5%). Ethyl

  18. Development of a dynamic headspace solid-phase microextraction procedure coupled to GC-qMSD for evaluation the chemical profile in alcoholic beverages.

    Science.gov (United States)

    Rodrigues, F; Caldeira, M; Câmara, J S

    2008-02-18

    In the present study, a simple and sensitive methodology based on dynamic headspace solid-phase microextraction (HS-SPME) followed by thermal desorption gas chromatography with quadrupole mass detection (GC-qMSD), was developed and optimized for the determination of volatile (VOCs) and semi-volatile (SVOCs) compounds from different alcoholic beverages: wine, beer and whisky. Key experimental factors influencing the equilibrium of the VOCs and SVOCs between the sample and the SPME fibre, as the type of fibre coating, extraction time and temperature, sample stirring and ionic strength, were optimized. The performance of five commercially available SPME fibres was evaluated and compared, namely polydimethylsiloxane (PDMS, 100 microm); polyacrylate (PA, 85 microm); polydimethylsiloxane/divinylbenzene (PDMS/DVB, 65 microm); carboxentrade mark/polydimethylsiloxane (CAR/PDMS, 75 microm) and the divinylbenzene/carboxen on polydimethylsiloxane (DVB/CAR/PDMS, 50/30 microm) (StableFlex). An objective comparison among different alcoholic beverages has been established in terms of qualitative and semi-quantitative differences on volatile and semi-volatile compounds. These compounds belong to several chemical families, including higher alcohols, ethyl esters, fatty acids, higher alcohol acetates, isoamyl esters, carbonyl compounds, furanic compounds, terpenoids, C13-norisoprenoids and volatile phenols. The optimized extraction conditions and GC-qMSD, lead to the successful identification of 44 compounds in white wines, 64 in beers and 104 in whiskys. Some of these compounds were found in all of the examined beverage samples. The main components of the HS-SPME found in white wines were ethyl octanoate (46.9%), ethyl decanoate (30.3%), ethyl 9-decenoate (10.7%), ethyl hexanoate (3.1%), and isoamyl octanoate (2.7%). As for beers, the major compounds were isoamyl alcohol (11.5%), ethyl octanoate (9.1%), isoamyl acetate (8.2%), 2-ethyl-1-hexanol (5.9%), and octanoic acid (5

  19. The study and applications of photochemical-dynamical gravity wave model Ⅱ-- The effects of stable gravity wave on chemical species distribution in mesosphere

    Institute of Scientific and Technical Information of China (English)

    XU; Jiyao(徐寄遥); MA; Ruiping(马瑞平); A.K.Smith

    2002-01-01

    A nonlinear, compressible, non-isothermal gravity wave model that involves photochemistry is used to study the effects of gravity wave on atmospheric chemical species distributions in this paper. The changes in the distributions of oxygen compound and hydrogen compound density induced by gravity wave propagation are simulated. The results indicate that when a gravity wave propagates through a mesopause region, even if it does not break, it can influence the background distributions of chemical species. The effect of gravity wave on chemical species at night is larger than in daytime.

  20. Molecular dynamics and quantum chemical calculation studies on 4,4-dimethyl-3-thiosemicarbazide as corrosion inhibitor in 2.5 M H{sub 2}SO{sub 4}

    Energy Technology Data Exchange (ETDEWEB)

    Musa, Ahmed Y., E-mail: ahmed.musa@ymail.com [Department of Chemical and Process Engineering, Universiti Kebangsaan Malaysia, Bangi 43600, Selangor (Malaysia); Kadhum, Abdul Amir H.; Mohamad, Abu Bakar; Takriff, Mohd Sobri [Department of Chemical and Process Engineering, Universiti Kebangsaan Malaysia, Bangi 43600, Selangor (Malaysia)

    2011-09-15

    Highlights: {yields} This work deals with a study of chemical additives for corrosion inhibition of mild steel in acidic conditions. {yields} The effects of the additive 4,4-dimethyl-3-thiosemicarbazide (DTS) on mild steel were studied by means of electrochemical techniques. {yields} Quantum chemical calculations and molecular dynamic model were performed to characterize the inhibition mechanism. {yields} The calculations provided information that helps in the analysis/interpretation of the experimental work. - Abstract: The inhibition of mild steel corrosion in a 2.5 M H{sub 2}SO{sub 4} solution by 4,4-dimethyl-3-thiosemicarbazide (DTS) was studied at 30 deg. C using potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). Quantum chemical parameters were calculated for DTS using PM3-SCF method. The molecular dynamic method was performed to simulate the adsorption of the DTS molecules on Fe surface. Results showed that DTS performed excellent as inhibitor for mild steel corrosion in a 2.5 M H{sub 2}SO{sub 4} solution and indicated that the inhibition efficiencies increase with the concentration of inhibitor. Theoretical results indicated that DTS could adsorb on the mild steel surface firmly through heteroatoms.

  1. Communication: Ro-vibrational control of chemical reactivity in H+CH{sub 4}→ H{sub 2}+CH{sub 3} : Full-dimensional quantum dynamics calculations and a sudden model

    Energy Technology Data Exchange (ETDEWEB)

    Welsch, Ralph, E-mail: rwelsch@uni-bielefeld.de; Manthe, Uwe, E-mail: uwe.manthe@uni-bielefeld.de [Theoretische Chemie, Fakultät für Chemie, Universität Bielefeld, Universitätsstr. 25, D-33615 Bielefeld (Germany)

    2014-08-07

    The mode-selective chemistry of the title reaction is studied by full-dimensional quantum dynamics simulation on an accurate ab initio potential energy surface for vanishing total angular momentum. Using a rigorous transition state based approach and multi-configurational time-dependent Hartree wave packet propagation, initial state-selected reaction probabilities for many ro-vibrational states of methane are calculated. The theoretical results are compared with experimental trends seen in reactions of methane. An intuitive interpretation of the ro-vibrational control of the chemical reactivity provided by a sudden model based on the quantum transition state concept is discussed.

  2. First steps towards probing chemical systems and dynamics with free-electron laser radiation--case studies at the FLASH facility

    Energy Technology Data Exchange (ETDEWEB)

    Hallmann, J; Gruebel, S; Rajkovic, I; Quevedo, W; Busse, G; Scholz, M; More, R; Petri, M; Techert, S, E-mail: stecher@gwdg.d [Max Planck Institute for Biophysical Chemistry, IFG Structural Dynamics of (Bio)chemical Systems, Am Fassberg 11, 37077 Goettingen (Germany)

    2010-10-14

    It is expected that free-electron laser (FEL) radiation with its unique properties will allow real-time tracking of structural changes during chemical reactions. The methods suggested being applied range from x-ray spectroscopy to diffraction. In order to reach this goal, in this work we will present our studies utilizing soft x-ray FEL radiation generated at the FLASH facility. We will present case studies of ultrafast x-ray diffraction on nanocrystalline lamellar assemblies of chemical relevance and heat dissipation studies on polymer foils (upon FLASH excitation) as revealed by ultrafast optical reflectivity. The extension of these studies to characterize in vacuum water jets during their interaction with FEL radiation will be given at the end if this overview. In conclusion, it can be stated that FLASH-FEL radiation can be used for studying chemical processes as long as the pulse duration is smaller than the characteristic time scales of destruction (ionization) and heat dissipation processes.

  3. Liberta o herói que há em ti: risco, mérito e transcendência no universo graffiti

    Directory of Open Access Journals (Sweden)

    Ricardo Campos

    2013-11-01

    Full Text Available Este artigo baseia-se numa pesquisa de natureza etnográfica realizada na área metropolitana de Lisboa, entre 2005 e 2007, cujo objeto é o graffiti urbano. Este é um contributo para o patrimônio de estudos dedicados à juventude, na medida em que aborda as questões de criatividade, agência e construção identitária num contexto social que, como diversas pesquisas têm demonstrado, é basicamente ocupado por indivíduos jovens. O risco e o gênio artístico são elementos que permitem avaliar o mérito de seus atores, fomentando a fabricação de uma representação do graffiti writer como um herói desalinhado, um virtuoso que se destaca do comum dos cidadãos. Seja pela vivência intensa do perigo na execução de graffiti ilegal em contextos ameaçadores, seja pela busca de uma linguagem estética singular e inovadora, o writer transcende fronteiras normativas e limitações pessoais. Argumentamos por isso que o graffiti é um fator de capacitação individual, um recurso vital na construção de identidades pessoais e coletivas à margem dos padrões hegemônicos.

  4. Age transcended: a semiotic and rhetorical analysis of the discourse of agelessness in North American anti-aging skin care advertisements.

    Science.gov (United States)

    Ellison, Kirsten L

    2014-04-01

    Drawing from a collection of over 160 North American print advertisements for anti-aging skin care products from January to December of 2009, this paper examines the discourse of agelessness, a vision of esthetic perfection and optimal health that is continually referred to by gerontologists, cultural theorists, and scientific researchers as a state of being to which humankind can aspire. Employing critical discourse analysis through the use of semiotics and visual rhetoric, this paper explores the means through which anti-aging skin care advertisements present to their viewers a particular object of desire, looking, more specifically, at how agelessness is presented as a way out and ultimate transcendence of age. Through the analytical tools of semiotics and visual rhetoric, four visions of agelessness are identified and explored in this paper: Agelessness as Scientific Purity, Agelessness as Genetic Impulse, Agelessness as Nature's Essence, and Agelessness as Myth. Whether found in the heights of scientific purity, the inner core of our genetic impulse, the depths of nature's essence, or whether agelessness itself has reached its own, untouchable, mythic status, the advertisements in this study represent one of the most pervasive vehicles through which our current vision(s) of ageless perfection are reflected, reinforced, and suspended in a drop of cream.

  5. Discussing the Transcendence of"Free Personality" to Individualism%论"自由个性"对个人主义的超越

    Institute of Scientific and Technical Information of China (English)

    刘兴盛

    2015-01-01

    马克思的"自由个性"思想超越了资本主义的个人主义,主要体现在马克思对资本主义的个人自由进行了前提、实质、结果的全面批判与解构,以及对个体与共同体相统一的彰显之中.揭示马克思"自由个性"思想对资本主义个人主义的这种超越,可以使我们在面对西方自由主义社会思潮的入侵和诘难时,做到有力地回击与批判.%Marx's free personality thought transcend the capitalist individualism. It is mainly reflected in the comprehensive criticism and deconstruction of the premise, the essence, the result of the individual freedom of capitalism, and the manifestation of the unity of the individual and the community. It can make us do a strong comeback and criticism when we confront the invasion of Western liberalism ideological and criticism to reveal Marx's free personality thought to the capitalist individualism.

  6. Connection between quantum systems involving the fourth Painlevé transcendent and k-step rational extensions of the harmonic oscillator related to Hermite exceptional orthogonal polynomial

    Energy Technology Data Exchange (ETDEWEB)

    Marquette, Ian, E-mail: i.marquette@uq.edu.au [School of Mathematics and Physics, The University of Queensland, Brisbane, QLD 4072 (Australia); Quesne, Christiane, E-mail: cquesne@ulb.ac.be [Physique Nucléaire Théorique et Physique Mathématique, Université Libre de Bruxelles, Campus de la Plaine CP229, Boulevard du Triomphe, B-1050 Brussels (Belgium)

    2016-05-15

    The purpose of this communication is to point out the connection between a 1D quantum Hamiltonian involving the fourth Painlevé transcendent P{sub IV}, obtained in the context of second-order supersymmetric quantum mechanics and third-order ladder operators, with a hierarchy of families of quantum systems called k-step rational extensions of the harmonic oscillator and related with multi-indexed X{sub m{sub 1,m{sub 2,…,m{sub k}}}} Hermite exceptional orthogonal polynomials of type III. The connection between these exactly solvable models is established at the level of the equivalence of the Hamiltonians using rational solutions of the fourth Painlevé equation in terms of generalized Hermite and Okamoto polynomials. We also relate the different ladder operators obtained by various combinations of supersymmetric constructions involving Darboux-Crum and Krein-Adler supercharges, their zero modes and the corresponding energies. These results will demonstrate and clarify the relation observed for a particular case in previous papers.

  7. Chemically Powered Nanomotors

    Science.gov (United States)

    Kapral, Raymond

    2007-03-01

    Molecular motors play important roles in transport in biological systems. These molecular machines are powered by chemical energy and operate in the regime of low Reynolds number hydrodynamics. Recently a class of simple inorganic molecular motors has been constructed and studied experimentally [1,2]. These motors are bimetallic rods, one end of which is chemically active. The talk will describe simple mesoscopic models for the motion of such nanomotors. The motor consists of two linked spheres, one of which catalyzes the conversion between two chemical species. The chemical species interact differently with the the two spheres in the dimer. The nano-dimer motor is solvated by a molecules treated at a mesoscopic level whose evolution is governed by multi-particle collision dynamics. The dynamics conserves mass, momentum and energy so that coupling between the nanomotor and the hydrodynamic modes of the solvent is treated correctly. The simulations allow one to explore the mechanisms of the chemically powered motion and the effects of fluctuations on the motor dynamics. [1] W. F. Paxton, et al., ``Catalytic Nanomotors: Autonomous Movement of Striped Nanorods,'' J. Am. Chem. Soc. (JACS), 126 (41), 13424 (2004). [2] S. Fournier-Bidoz, et al. ``Synthetic Self-Propelled Nanorotors,'' Chem. Commun., (4), 441 (2005).

  8. Chemical use

    Data.gov (United States)

    US Fish and Wildlife Service, Department of the Interior — This is a summary of research and activities related to chemical use on Neal Smith National Wildlife Refuge between 1992 and 2009. The chemicals used on the Refuge...

  9. Chemical Peel

    Science.gov (United States)

    ... 20, 2015. Anitha B. Prevention of complications in chemical peeling. Journal of Cutaneous and Aesthetic Surgery. 2010;3:186. Langsdon PR, et al. Latest chemical peel innovations. Facial and Plastic Surgery Clinics of ...

  10. Chemical Reactors.

    Science.gov (United States)

    Kenney, C. N.

    1980-01-01

    Describes a course, including content, reading list, and presentation on chemical reactors at Cambridge University, England. A brief comparison of chemical engineering education between the United States and England is also given. (JN)

  11. Application of dynamic electronic track scale in liquid chemical products%动态轨道衡在液体化工产品计量上的应用

    Institute of Scientific and Technical Information of China (English)

    赵联毅

    2014-01-01

    石油化工企业的大量液体产品需要使用铁路罐车进行运输,由于传统的人工手检尺方式计量准确度差、效率低,许多企业逐步使用轨道衡进行铁路罐车的计量工作。本文以石脑油产品为例,介绍动态电子轨道衡在企业计量工作中的应用情况。%A great quantity of liquid chemical products in petrochemical enterprise require transporting by rail tank cars.The traditional manual measuring is of low accuracy and efficiency,which makes a great many enterprises use dynamic electronic track scale to measure rail tank cars. Taking naphtha as an instance ,this paper introduces the application of dynamic electronic track scale in liquid chemical products.

  12. The Reference and Transcendence of Religion to Ideological and Political Education in University%高校思想政治教育对宗教信仰的借鉴与超越∗

    Institute of Scientific and Technical Information of China (English)

    周丽芳

    2014-01-01

    There are value consensus and essential differences between Ideological and political ed-ucation and religion,thus this paper puts forward the rationality of drawing lessons from religion and the necessity of transcending to religion .Ideological and political education can learn from religion to realize the harmonious unification of education targeted of the ultimate and gradation levels,to realize the combination of the external social reflection and the inner life view,to realize the goal of Marx's religious belief by the means of science.Ideological and political education should transcend religious gods on world outlook with dialectical materialism world outlook,transcend the other side of the world fantasy with reality contemplation,and transcend the mystical experience religious with the ra-tional practice.The reference and transcendence of ideological and political education of university to religion will get more education successive experience and cultural resources,and consolidate the sta-tus and role of the socialist core value idea.%思想政治教育与宗教信仰有价值共契也有本质差异,由此提出思想政治教育对宗教信仰借鉴的合理性以及超越的必要性。思想政治教育可以借鉴宗教信仰,实现教育目标终极性与层次性的和谐统一,实现外部的社会观照与内部的人生观照的结合,确立马克思主义信仰目标宗教化与实现手段科学化的统一。思想政治教育要超越宗教神灵论的世界观代之以辩证唯物主义的世界观,超越彼岸世界的幻想代之以现实的观照,超越宗教的神秘体验代之以理性实践。高校思想理论教育对宗教的借鉴与超越,将会获取更多经验和文化资源,切实保障社会主义核心价值理念的地位与作用。

  13. Antimalarial efficacy of dynamic compound of plumbagin chemical constituent from Plumbago zeylanica Linn (Plumbaginaceae) against the malarial vector Anopheles stephensi Liston (Diptera: Culicidae).

    Science.gov (United States)

    Pradeepa, Venkatraman; Sathish-Narayanan, Subbiah; Kirubakaran, Suyambulingam Arunachalam; Senthil-Nathan, Sengottayan

    2014-08-01

    In the present investigation, the effective root compound of plumbagin of Plumbago zeylanica (Plumbaginaceae) was evaluated for chemical constituent and antimalarial effect against the fourth instar larvae of Anopheles stephensi Liston (Diptera). In the chromatographic analyses of root compound with Rf value of 0.788 and NMR analyses also revealed that the effective compound contain naphthoquinone plumbagin were identified as the major chemical constituent. Larval mortality was observed after 3 h of exposure period. The plumbagin compound showed remarkable larvicidal activity against A. stephensi (LC50 32.65 and LC9072.27 ppm). Histopathological effects of compound was observed in the treated larvae. Based on the results, the plumbagin compound of P. zeylanica can be considered as a new source of natural larvicide for the control of malarial vector.

  14. A bionics chemical synapse.

    Science.gov (United States)

    Thanapitak, Surachoke; Toumazou, Christofer

    2013-06-01

    Implementation of the current mode CMOS circuit for chemical synapses (AMPA and NMDA receptors) with dynamic change of glutamate as the neurotransmitter input is presented in this paper. Additionally, circuit realisation for receptor GABA(A) and GABA(B) with an electrical signal which symbolises γ-Aminobutyric Acid (GABA) perturbation is introduced. The chemical sensor for glutamate sensing is the modified ISFET with enzyme (glutamate oxidase) immobilisation. The measured results from these biomimetics chemical synapse circuits closely match with the simulation result from the mathematical model. The total power consumption of the whole chip (four chemical synapse circuits and all auxiliary circuits) is 168.3 μW. The total chip area is 3 mm(2) in 0.35-μm AMS CMOS technology.

  15. Investigation of Spark Ignition and Autoignition in Methane and Air Using Computational Fluid Dynamics and Chemical Reaction Kinetics. A numerical Study of Ignition Processes in Internal Combustion Engines

    Energy Technology Data Exchange (ETDEWEB)

    Nordrik, R.

    1993-12-01

    The processes in the combustion chamber of internal combustion engines have received increased attention in recent years because their efficiencies are important both economically and environmentally. This doctoral thesis studies the ignition phenomena by means of numerical simulation methods. The fundamental physical relations include flow field conservation equations, thermodynamics, chemical reaction kinetics, transport properties and spark modelling. Special attention is given to the inclusion of chemical kinetics in the flow field equations. Using his No Transport of Radicals Concept method, the author reduces the computational efforts by neglecting the transport of selected intermediate species. The method is validated by comparison with flame propagation data. A computational method is described and used to simulate spark ignition in laminar premixed methane-air mixtures and the autoignition process of a methane bubble surrounded by hot air. The spark ignition simulation agrees well with experimental results from the literature. The autoignition simulation identifies the importance of diffusive and chemical processes acting together. The ignition delay times exceed the experimental values found in the literature for premixed ignition delay, presumably because of the mixing process and lack of information on low temperature reactions in the skeletal kinetic mechanism. Transient turbulent methane jet autoignition is simulated by means of the KIVA-II code. Turbulent combustion is modelled by the Eddy Dissipation Concept. 90 refs., 81 figs., 3 tabs.

  16. A comparative study of the chemical and integrated treatments impact against the defoliating insects on the structure and dynamics of the edaphic mesofauna in two oak forests from North-Eastern Romania

    Directory of Open Access Journals (Sweden)

    Adina Cãlugãr

    2009-11-01

    Full Text Available The author presents in this paper some aspects about the edaphicmicroarthropods from the organic horizon of two forest soils belonging to the Ciurea Forest District, Iasi County: ªanta (mixed stands mainly with oak, chemically treated against defoliating insects and Poieni - Tomesti (Quercus robur and Quercuspetraea stands with integrated treatments. The study of edaphic microarthropods was performed both from qualitative and quantitative point of view. It considered the average of the total density of the microarthropod populations and by each taxonomic group, according to stations and subhorizons, as well as the ratio between thetaxonomical and trophic groups. The investigations concerning edaphic mesofauna consist in inventory and analysis of the mites belonging to Oribatida, Gamasida, Actinedida and Acaridida orders, of the Collembola, as well as other insects; other groups of microarthropods were taken into consideration too (pseudoscorpiones,myriapods etc. The consequences of the treatments against the defoliators on theedaphic mesofauna were performed at four different moments. Generally, lower densities were observed in the case of the chemically treated stands. The communities of the edaphic mesofauna from the integrated management treated stands are more stableduring the time. In the chemically treated stands, the densities of the microartropods vary between large limits; this instability could be assigned to this kind of treatment. The vertical distribution of the mesofauna depends on the textural characteristics of the soil, being at the same time a dynamic parameter that is modifyed according to the variation of the climatic factors.

  17. On Marx’s Criticism and Transcendence of Historicism%论马克思对历史主义的批判和超越

    Institute of Scientific and Technical Information of China (English)

    曹蓓蓓

    2016-01-01

    In the contemporary understanding of historical materialism ,the relationship between historical materialism and historicism will be involved in the understanding of its spiritual essence .Historicism ,by its ideological essence ,opposes universalism ,draw s on and draw s lessons from the natural sciences ,takes the subject and the object as the basic framework ,attaches importance to the study of historical facts rath-er than the analysis of historical law s ,emphasizing the future by grasping the past .Marx is different from historicism ,w hich emphasizes the law of history ,and also analyzes the temporary nature of capitalism ,so Marx achieves a critical transcendence of historicism on the basis of understanding history .%在对唯物史观的当代性理解中,在理解其精神实质时会涉及到唯物史观与历史主义的关系问题。历史主义按其思想本质来说,它反对普遍主义,吸取与借鉴自然科学的方法,以主客二分为基本架构,重视史实的研究而非历史规律的分析,主要是强调通过理解过去来把握未来。而马克思有别于历史主义,马克思强调历史规律,也分析了资本主义的暂时性,故而马克思在对历史的理解上实现了对历史主义的批判性超越。

  18. Induction of strain-transcendent antibodies to placental-type isolates with VAR2CSA DBL3 or DBL5 recombinant proteins

    Directory of Open Access Journals (Sweden)

    Hathaway Marianne J

    2011-02-01

    Full Text Available Abstract Background Pregnancy associated malaria is a severe clinical syndrome associated with sequestration of Plasmodium falciparum-infected erythrocytes in the placenta. Placental binding is mediated by VAR2CSA, which adheres to chondroitin sulphate A (CSA. VAR2CSA is a large and polymorphic protein that has six Duffy binding-like (DBL domains. There is still limited understanding as to how effective individual VAR2CSA domains are at generating inhibitory antibodies or the number of domain variants needed for universal vaccine coverage. Methods To investigate the immunogenic properties of single domain VAR2CSA recombinant proteins, rats or rabbits were immunized with five of the six VAR2CSA domains produced in Pichia pastoris. Immune plasma was analysed against a geographically diverse panel of CSA-binding lab lines to assess antibody breadth and inhibitory activity. Results Of the five domains, DBL3, and to a lesser extent DBL5, induced antibodies that cross-reacted on five diverse CSA-binding parasite lines by flow cytometry. By comparison, anti-DBL6 antibodies were highly strain-specific and anti-DBL1 and anti-DBL4 antibodies were poorly reactive by flow cytometry. From this series of recombinant proteins, adhesion-blocking activity was restricted to a single rat immunized against a DBL4 recombinant protein. Conclusions Single domain VAR2CSA recombinant proteins produced in P. pastoris had limited efficacy in eliciting adhesion blocking antibody responses, but VAR2CSA DBL3 and DBL5 domains contain strain-transcendent epitopes that can be targeted by vaccination and may have application for vaccine development.

  19. Exact solutions for chemical concentration waves of self-propelling camphor particles racing on a ring: A novel potential dynamics perspective

    CERN Document Server

    Frank, T D

    2015-01-01

    A potential dynamics approach is developed to determine the periodic standing and traveling wave patterns associated with self-propelling camphor objects floating on ring-shaped water channels. Exact solutions of the wave patterns are derived. The bifurcation diagram describing the transition between the immobile and self-propelling modes of camphor objects is derived semi-analytically. The bifurcation is of a pitchfork type which is consistent with earlier theoretical work in which natural boundary conditions have been considered.

  20. Development of a dynamic headspace solid-phase microextraction procedure coupled to GC–qMSD for evaluation the chemical profile in alcoholic beverages

    OpenAIRE

    Rodrigues, F.; Caldeira, M; Câmara, José de Sousa

    2008-01-01

    In the present study, a simple and sensitive methodology based on dynamic headspace solid-phase microextraction (HS-SPME) followed by thermal desorption gas chromatography with quadrupole mass detection (GC–qMSD), was developed and optimized for the determination of volatile (VOCs) and semi-volatile (SVOCs) compounds from different alcoholic beverages: wine, beer and whisky. Key experimental factors influencing the equilibrium of the VOCs and SVOCs between the sample and the SPME fibre, as th...