WorldWideScience

Sample records for chemical dynamics studies

  1. Studies in Chemical Dynamics

    International Nuclear Information System (INIS)

    Rabitz, Herschel; Ho, Tak-San

    2003-01-01

    This final report draws together the research carried from February, 1986 through January, 2003 concerning a series of topics in chemical dynamics. The specific areas of study include molecular collisions, chemical kinetics, data inversion to extract potential energy surfaces, and model reduction of complex kinetic systems

  2. Gas-Phase Molecular Dynamics: Theoretical Studies in Spectroscopy and Chemical Dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Yu, H.G.; Muckerman, J.T.

    2010-06-01

    The goal of this program is the development and application of computational methods for studying chemical reaction dynamics and molecular spectroscopy in the gas phase. We are interested in developing rigorous quantum dynamics algorithms for small polyatomic systems and in implementing approximate approaches for complex ones. Particular focus is on the dynamics and kinetics of chemical reactions and on the rovibrational spectra of species involved in combustion processes. This research also explores the potential energy surfaces of these systems of interest using state-of-the-art quantum chemistry methods.

  3. Gas-Phase Molecular Dynamics: Theoretical Studies In Spectroscopy and Chemical Dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Yu H. G.; Muckerman, J.T.

    2012-05-29

    The main goal of this program is the development and application of computational methods for studying chemical reaction dynamics and molecular spectroscopy in the gas phase. We are interested in developing rigorous quantum dynamics algorithms for small polyatomic systems and in implementing approximate approaches for complex ones. Particular focus is on the dynamics and kinetics of chemical reactions and on the rovibrational spectra of species involved in combustion processes. This research also explores the potential energy surfaces of these systems of interest using state-of-the-art quantum chemistry methods, and extends them to understand some important properties of materials in condensed phases and interstellar medium as well as in combustion environments.

  4. 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.

  5. 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...

  6. Photocatalytic oxidation dynamics of acetone on TiO2: tight-binding quantum chemical molecular dynamics study

    International Nuclear Information System (INIS)

    Lv Chen; Wang Xiaojing; Agalya, Govindasamy; Koyama, Michihisa; Kubo, Momoji; Miyamoto, Akira

    2005-01-01

    The clarification of the excited states dynamics on TiO 2 surface is important subject for the design of the highly active photocatalysts. In the present study, we applied our novel tight-binding quantum chemical molecular dynamics method to the investigation on the photocatalytic oxidation dynamics of acetone by photogenerated OH radicals on the hydrated anatase TiO 2 surface. The elucidated photocatalytic reaction mechanism strongly supports the previous experimental proposal and finally the effectiveness of our new approach for the clarification of the photocatalytic reaction dynamics employing the large simulation model was confirmed

  7. 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.

  8. Chemical reaction dynamics using the Advanced Light Source

    International Nuclear Information System (INIS)

    Yang, X.; Blank, D.A.; Heimann, P.A.; Lee, Y.T.; Suits, A.G.; Lin, J.; Wodtke, A.M.

    1995-01-01

    The recently commissioned Advanced Light Source (ALS) at Berkeley provides a high brightness, tunable VUV light source for chemical dynamics studies. A dedicated chemical dynamics beamline has been built at the ALS for studies of fundamental chemical processes. High flux (10(sup 16) photon/s with 2% bandwidth) VUV synchrotron radiation from 5 to 30 eV can be obtained from the beamline, whose source is the U8/10 undulator. Three endstations will be in operation for studies ranging from crossed beam reaction dynamics and photodissociation to high resolution photoionization dynamics and spectroscopy. A rotatable source crossed molecular beam apparatus (endstation one) has been established for unimolecular and bimolecular reactive scattering studies. Photodissociation of methylamine and ozone were carried out using VUV synchrotron radiation as the ionization detection technique at this endstation. Results show the advantages of the new endstation using VUV ionization as the detection scheme over similar machines using electron bombardment as the ionization source

  9. Chemical reaction dynamics using the Advanced Light Source

    International Nuclear Information System (INIS)

    Yang, X.; Blank, D.A.; Heimann, P.A.; Lee, Y.T.; Suits, A.G.; Lin, J.; Wodtke, A.M.

    1995-09-01

    The recently commissioned Advanced Light Source (ALS) at Berkeley provides a high brightness, tunable VUV light source for chemical dynamics studies. A dedicated chemical dynamics beamline has been built at the ALS for studies of fundamental chemical processes. High flux (10 16 photon/s with 2% bandwidth) VUV synchrotron radiation from 5 to 30 eV can be obtained from the beamline, whose source is the U8/10 undulator. Three endstations will be in operation for studies ranging from crossed beam reaction dynamics and photodissociation to high resolution photoionization dynamics and spectroscopy. A rotatable source crossed molecular beam apparatus (endstation one) has been established for unimolecular and bimolecular reactive scattering studies. Photodissociation of methylamine and ozone were carried out using VUV synchrotron radiation as the ionization detection technique at this endstation. Results show the advantages of the new endstation using VUV ionization as the detection scheme over similar machines using electron bombardment as the ionization source

  10. Chemical Dynamics at the Advanced Light Source

    International Nuclear Information System (INIS)

    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.

    1999-01-01

    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

  11. 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.

  12. Chemical structure and dynamics: Annual report 1996

    International Nuclear Information System (INIS)

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

    1997-03-01

    The Chemical Structure and Dynamics (CS ampersand 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

  13. 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.

  14. Molecular dynamics simulations of solutions at constant chemical potential

    Science.gov (United States)

    Perego, C.; Salvalaglio, M.; Parrinello, M.

    2015-04-01

    Molecular dynamics studies of chemical processes in solution are of great value in a wide spectrum of applications, which 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, which 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 Constant Chemical Potential Molecular Dynamics (CμMD) 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 CμMD method to the paradigmatic case of urea crystallization in aqueous solution. As a result, we have been able to study crystal growth dynamics under constant supersaturation conditions and to extract growth rates and free-energy barriers.

  15. Development of a quantum chemical molecular dynamics tribochemical simulator and its application to tribochemical reaction dynamics of lubricant additives

    International Nuclear Information System (INIS)

    Onodera, T; Tsuboi, H; Hatakeyama, N; Endou, A; Miyamoto, A; Miura, R; Takaba, H; Suzuki, A; Kubo, M

    2010-01-01

    Tribology at the atomistic and molecular levels has been theoretically studied by a classical molecular dynamics (MD) method. However, this method inherently cannot simulate the tribochemical reaction dynamics because it does not consider the electrons in nature. Although the first-principles based MD method has recently been used for understanding the chemical reaction dynamics of several molecules in the tribology field, the method cannot simulate the tribochemical reaction dynamics of a large complex system including solid surfaces and interfaces due to its huge computation costs. On the other hand, we have developed a quantum chemical MD tribochemical simulator on the basis of a hybrid tight-binding quantum chemical/classical MD method. In the simulator, the central part of the chemical reaction dynamics is calculated by the tight-binding quantum chemical MD method, and the remaining part is calculated by the classical MD method. Therefore, the developed tribochemical simulator realizes the study on tribochemical reaction dynamics of a large complex system, which cannot be treated by using the conventional classical MD or the first-principles MD methods. In this paper, we review our developed quantum chemical MD tribochemical simulator and its application to the tribochemical reaction dynamics of a few lubricant additives

  16. Development of tight-binding, chemical-reaction-dynamics simulator for combinatorial computational chemistry

    International Nuclear Information System (INIS)

    Kubo, Momoji; Ando, Minako; Sakahara, Satoshi; Jung, Changho; Seki, Kotaro; Kusagaya, Tomonori; Endou, Akira; Takami, Seiichi; Imamura, Akira; Miyamoto, Akira

    2004-01-01

    Recently, we have proposed a new concept called 'combinatorial computational chemistry' to realize a theoretical, high-throughput screening of catalysts and materials. We have already applied our combinatorial, computational-chemistry approach, mainly based on static first-principles calculations, to various catalysts and materials systems and its applicability to the catalysts and materials design was strongly confirmed. In order to realize more effective and efficient combinatorial, computational-chemistry screening, a high-speed, chemical-reaction-dynamics simulator based on quantum-chemical, molecular-dynamics method is essential. However, to the best of our knowledge, there is no chemical-reaction-dynamics simulator, which has an enough high-speed ability to perform a high-throughput screening. In the present study, we have succeeded in the development of a chemical-reaction-dynamics simulator based on our original, tight-binding, quantum-chemical, molecular-dynamics method, which is more than 5000 times faster than the regular first-principles, molecular-dynamics method. Moreover, its applicability and effectiveness to the atomistic clarification of the methanol-synthesis dynamics at reaction temperature were demonstrated

  17. 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.

  18. 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.

  19. 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.

  20. Chemical Structure and Dynamics annual report 1997

    International Nuclear Information System (INIS)

    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

  1. 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.

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

    International Nuclear Information System (INIS)

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

    2010-01-01

    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.

  3. 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.

  4. 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).

  5. A network dynamics approach to chemical reaction networks

    Science.gov (United States)

    van der Schaft, A. J.; Rao, S.; Jayawardhana, B.

    2016-04-01

    A treatment of a chemical reaction network theory is given from the perspective of nonlinear network dynamics, in particular of consensus dynamics. By starting from the complex-balanced assumption, the reaction dynamics governed by mass action kinetics can be rewritten into a form which allows for a very simple derivation of a number of key results in the chemical reaction network theory, and which directly relates to the thermodynamics and port-Hamiltonian formulation of the system. Central in this formulation is the definition of a balanced Laplacian matrix on the graph of chemical complexes together with a resulting fundamental inequality. This immediately leads to the characterisation of the set of equilibria and their stability. Furthermore, the assumption of complex balancedness is revisited from the point of view of Kirchhoff's matrix tree theorem. Both the form of the dynamics and the deduced behaviour are very similar to consensus dynamics, and provide additional perspectives to the latter. Finally, using the classical idea of extending the graph of chemical complexes by a 'zero' complex, a complete steady-state stability analysis of mass action kinetics reaction networks with constant inflows and mass action kinetics outflows is given, and a unified framework is provided for structure-preserving model reduction of this important class of open reaction networks.

  6. 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.

  7. Nanomotor dynamics in a chemically oscillating medium

    International Nuclear Information System (INIS)

    Robertson, Bryan; Kapral, Raymond

    2015-01-01

    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

  8. 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. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Hydration structure and dynamics of a hydroxide ion in water clusters of varying size and temperature: Quantum chemical and ab initio molecular dynamics studies

    International Nuclear Information System (INIS)

    Bankura, Arindam; Chandra, Amalendu

    2012-01-01

    Highlights: ► A theoretical study of hydroxide ion-water clusters is carried for varying cluster size and temperature. ► The structures of OH − (H 2 O) n are found out through quantum chemical calculations for n = 4, 8, 16 and 20. ► The finite temperature behavior of the clusters is studied through ab initio dynamical simulations. ► The spectral features of OH modes (deuterated) and their dependence on hydrogen bonding states of water are discussed. ► The mechanism and kinetics of proton transfer processes in these anionic clusters are also investigated. - Abstract: We have investigated the hydration structure and dynamics of OH − (H 2 O) n clusters (n = 4, 8, 16 and 20) by means of quantum chemical and ab initio molecular dynamics calculations. Quantum chemical calculations reveal that the solvation structure of the hydroxide ion transforms from three and four-coordinated surface states to five-coordinated interior state with increase in cluster size. Several other isomeric structures with energies not very different from the most stable isomer are also found. Ab initio simulations show that the most probable configurations at higher temperatures need not be the lowest energy isomeric structure. The rates of proton transfer in these clusters are found to be slower than that in bulk water. The vibrational spectral calculations reveal distinct features for free OH (deuterated) stretch modes of water in different hydrogen bonding states. Effects of temperature on the structural and dynamical properties are also investigated for the largest cluster considered here.

  10. Catalytic performances of chemically immobilized urease under static and dynamic conditions: A comparative study

    OpenAIRE

    Yürekli, Yılmaz; Alsoy Altınkaya, Sacide

    2011-01-01

    Immobilized urease has been used for direct removal of urea from aqueous solution and as biological sensing material in the preparation of urea biosensors. The former application is carried out under dynamic condition using ultrafiltration membrane either in tubular form or in flat sheet, while the latter is used in static condition. In this study, the performance of chemically immobilized urease on poly(acrylonitrile-co-sodium methallyl sulfonate) ultrafiltration membrane was determined unde...

  11. 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.

  12. Special Issue on Theoretical Chemistry/Chemical Dynamics

    Indian Academy of Sciences (India)

    2017-07-02

    Jul 2, 2017 ... This month's issue of the Journal of Chemical Sciences honours Professor Charusita Chakravarty, who has made immeasurable contributions to theoretical chemistry and chemical dynamics. The editors Biman Bagchi (FASc, FNA, FTWAS; Indian Institute of Science, Bangalore, India), David Clary (FRS; ...

  13. 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

  14. Annual Report 2000. Chemical Structure and Dynamics; FINAL

    International Nuclear Information System (INIS)

    Colson, Steve D; McDowell, Rod S

    2001-01-01

    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 and 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

  15. A network dynamics approach to chemical reaction networks

    NARCIS (Netherlands)

    van der Schaft, Abraham; Rao, S.; Jayawardhana, B.

    2016-01-01

    A treatment of chemical reaction network theory is given from the perspective of nonlinear network dynamics, in particular of consensus dynamics. By starting from the complex-balanced assumption the reaction dynamics governed by mass action kinetics can be rewritten into a form which allows for a

  16. Molecular dynamics simulation of a chemical reaction

    International Nuclear Information System (INIS)

    Gorecki, J.; Gryko, J.

    1988-06-01

    Molecular dynamics is used to study the chemical reaction A+A→B+B. It is shown that the reaction rate constant follows the Arrhenius law both for Lennard-Jones and hard sphere interaction potentials between substrate particles. A. For the denser systems the reaction rate is proportional to the value of the radial distribution function at the contact point of two hard spheres. 10 refs, 4 figs

  17. Amorphization induced by chemical disorder in crystalline NiZr2: A molecular-dynamics study based on an n-body potential

    International Nuclear Information System (INIS)

    Massobrio, C.; Pontikis, V.; Martin, G.

    1989-01-01

    We present the first molecular-dynamics study of the amorphization of a crystalline alloy (NiZr 2 ) induced by chemical disorder. We used a n-body potential in conjunction with isobaric-isothermal molecular dynamics. The behavior of the pair distribution function suggests that the instability leading to the amorphous state is a first-order phase transformation

  18. Dynamic Processes of Conceptual Change: Analysis of Constructing Mental Models of Chemical Equilibrium.

    Science.gov (United States)

    Chiu, Mei-Hung; Chou, Chin-Cheng; Liu, Chia-Ju

    2002-01-01

    Investigates students' mental models of chemical equilibrium using dynamic science assessments. Reports that students at various levels have misconceptions about chemical equilibrium. Involves 10th grade students (n=30) in the study doing a series of hands-on chemical experiments. Focuses on the process of constructing mental models, dynamic…

  19. Control of chemical dynamics by lasers: theoretical considerations.

    Science.gov (United States)

    Kondorskiy, Alexey; Nanbu, Shinkoh; Teranishi, Yoshiaki; Nakamura, Hiroki

    2010-06-03

    Theoretical ideas are proposed for laser control of chemical dynamics. There are the following three elementary processes in chemical dynamics: (i) motion of the wave packet on a single adiabatic potential energy surface, (ii) excitation/de-excitation or pump/dump of wave packet, and (iii) nonadiabatic transitions at conical intersections of potential energy surfaces. A variety of chemical dynamics can be controlled, if we can control these three elementary processes as we desire. For (i) we have formulated the semiclassical guided optimal control theory, which can be applied to multidimensional real systems. The quadratic or periodic frequency chirping method can achieve process (ii) with high efficiency close to 100%. Concerning process (iii) mentioned above, the directed momentum method, in which a predetermined momentum vector is given to the initial wave packet, makes it possible to enhance the desired transitions at conical intersections. In addition to these three processes, the intriguing phenomenon of complete reflection in the nonadiabatic-tunneling-type of potential curve crossing can also be used to control a certain class of chemical dynamics. The basic ideas and theoretical formulations are provided for the above-mentioned processes. To demonstrate the effectiveness of these controlling methods, numerical examples are shown by taking the following processes: (a) vibrational photoisomerization of HCN, (b) selective and complete excitation of the fine structure levels of K and Cs atoms, (c) photoconversion of cyclohexadiene to hexatriene, and (d) photodissociation of OHCl to O + HCl.

  20. molecular dynamics simulations and quantum chemical calculations

    African Journals Online (AJOL)

    ABSTRACT. The molecular dynamic (MD) simulation and quantum chemical calculations for the adsorption of [2-(2-Henicos-10- .... electronic properties of molecule clusters, surfaces and ... The local reactivity was analyzed by determining the.

  1. 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...

  2. Dynamics of chemical equilibrium of hadronic matter close to Tc

    International Nuclear Information System (INIS)

    Noronha-Hostler, J.; Beitel, M.; Greiner, C.; Shovkovy, I.

    2010-01-01

    Quick chemical equilibration times of hadrons (specifically, pp-bar, KK-bar, ΛΛ-bar, and ΩΩ-bar pairs) within a hadron gas are explained dynamically using Hagedorn states, which drive particles into equilibrium close to the critical temperature. Within this scheme, we use master equations and derive various analytical estimates for the chemical equilibration times. We compare our model to recent lattice results and find that for both T c =176 MeV and T c =196 MeV, the hadrons can reach chemical equilibrium almost immediately, well before the chemical freeze-out temperatures found in thermal fits for a hadron gas without Hagedorn states. Furthermore, the ratios p/π, K/π, Λ/π, and Ω/π match experimental values well in our dynamical scenario.

  3. DYNSIR; A dynamic simulator for the chemical process

    International Nuclear Information System (INIS)

    Park, Hyun Soo; Yoo, Jae Hyung; Byeon, Kee Hoh; Park, Jeong Hwa; Park, Seong Won

    1990-03-01

    A program code for dynamic simulation of arbitrary chemical process, called DYNSIR, is developed. The code can simulate rather arbitrary arrangements of individual chemical processing units whose models are described by ordinary differential equations. The code structure to handle input/output, memory and data management, numerical interactive or predetermined changes in parameter values during the simulation. Individual model is easy to maintain since the modular approach is used. The integration routine is highly effective because of the development of algorithm for modular integration method using the cubic spline. DYNSIR's data structures are not the index but the pointer structure. This pointer structure allows the dynamic memory allocation for the memory management. The dynamic memory allocation methods is to minimize the amount of memories and to overcome the limitation of the number of variables to be used. Finally, it includes various functions, such as the input preprocessor, the effective error processing, and plotting and reporting routines. (author)

  4. The Dynamics of Chemical Reactions: Atomistic Visualizations of Organic Reactions, and Homage to van 't Hoff.

    Science.gov (United States)

    Yang, Zhongyue; Houk, K N

    2018-03-15

    Jacobus Henricus van 't Hoff was the first Nobel Laureate in Chemistry. He pioneered in the study of chemical dynamics, which referred at that time to chemical kinetics and thermodynamics. The term has evolved in modern times to refer to the exploration of chemical transformations in a time-resolved fashion. Chemical dynamics has been driven by the development of molecular dynamics trajectory simulations, which provide atomic visualization of chemical processes and illuminate how dynamic effects influence chemical reactivity and selectivity. In homage to the legend of van 't Hoff, we review the development of the chemical dynamics of organic reactions, our area of research. We then discuss our trajectory simulations of pericyclic reactions, and our development of dynamic criteria for concerted and stepwise reaction mechanisms. We also describe a method that we call environment-perturbed transition state sampling, which enables trajectory simulations in condensed-media using quantum mechanics and molecular mechanics (QM/MM). We apply the method to reactions in solvent and in enzyme. Jacobus Henricus van 't Hoff (1852, Rotterdam-1911, Berlin) received the Nobel Prize for Chemistry in 1901 "in recognition of the extraordinary services he has rendered by the discovery of the laws of chemical dynamics and osmotic pressure in solutions". van 't Hoff was born the Netherlands, and earned his doctorate in Utrecht in 1874. In 1896 he moved to Berlin, where he was offered a position with more research and less teaching. van 't Hoff is considered one of the founders of physical chemistry. A key step in establishing this new field was the start of Zeitschrift für Physikalische Chemie in 1887. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Molecular beam studies of reaction dynamics

    International Nuclear Information System (INIS)

    Lee, Yuan T.

    1991-03-01

    The major thrust of this research project is to elucidate detailed dynamics of simple elementary reactions that are theoretically important and to unravel the mechanism of complex chemical reactions or photochemical processes that play important roles in many macroscopic processes. Molecular beams of reactants are used to study individual reactive encounters between molecules or to monitor photodissociation events in a collision-free environment. Most of the information is derived from measurement of the product fragment energy, angular, and state distributions. Recent activities are centered on the mechanisms of elementary chemical reactions involving oxygen atoms with unsaturated hydrocarbons, the dynamics of endothermic substitution reactions, the dependence of the chemical reactivity of electronically excited atoms on the alignment of excited orbitals, the primary photochemical processes of polyatomic molecules, intramolecular energy transfer of chemically activated and locally excited molecules, the energetics of free radicals that are important to combustion processes, the infrared-absorption spectra of carbonium ions and hydrated hydronium ions, and bond-selective photodissociation through electric excitation

  6. Molecular beam studies of reaction dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Y.T. [Lawrence Berkeley Laboratory, CA (United States)

    1993-12-01

    The major thrust of this research project is to elucidate detailed dynamics of simple elementary reactions that are theoretically important and to unravel the mechanism of complex chemical reactions or photochemical processes that play important roles in many macroscopic processes. Molecular beams of reactants are used to study individual reactive encounters between molecules or to monitor photodissociation events in a collision-free environment. Most of the information is derived from measurement of the product fragment energy, angular, and state distributions. Recent activities are centered on the mechanisms of elementary chemical reactions involving oxygen atoms with unsaturated hydrocarbons, the dynamics of endothermic substitution reactions, the dependence of the chemical reactivity of electronically excited atoms on the alignment of excited orbitals, the primary photochemical processes of polyatomic molecules, intramolecular energy transfer of chemically activated and locally excited molecules, the energetics of free radicals that are important to combustion processes, the infrared-absorption spectra of carbonium ions and hydrated hydronium ions, and bond-selective photodissociation through electric excitation.

  7. 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

    material source-segregation and collection was the least effective strategy for reducing chemical contamination, if the overall recycling rates should be maintained at the current level (approximately 70% for Europe). The study provides a consistent approach for evaluating contaminant levels in material......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...... cycle. The approach combines static material flow analysis (MFA) with dynamic material and substance flow modeling. The results indicate that phasing out of chemicals is the most effective measure for reducing chemical contamination. However, this scenario was also associated with a considerable lag...

  8. 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.

  9. 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...... such as electron(7-10) or X-ray diffraction(11) and X-ray absorption(12) yield complementary information about the atomic motions. Time-resolved methods that are directly sensitive to both valence-electron dynamics and atomic motions include photoelectron spectroscopy(13-15) and high-harmonic generation(16......,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...

  10. The development and application of dynamic operational risk assessment in oil/gas and chemical process industry

    International Nuclear Information System (INIS)

    Yang Xiaole; Mannan, M. Sam

    2010-01-01

    A methodology of dynamic operational risk assessment (DORA) is proposed for operational risk analysis in oil/gas and chemical industries. The methodology is introduced comprehensively starting from the conceptual framework design to mathematical modeling and to decision making based on cost-benefit analysis. The probabilistic modeling part of DORA integrates stochastic modeling and process dynamics modeling to evaluate operational risk. The stochastic system-state trajectory is modeled according to the abnormal behavior or failure of each component. For each of the possible system-state trajectories, a process dynamics evaluation is carried out to check whether process variables, e.g., level, flow rate, temperature, pressure, or chemical concentration, remain in their desirable regions. Component testing/inspection intervals and repair times are critical parameters to define the system-state configuration, and play an important role for evaluating the probability of operational failure. This methodology not only provides a framework to evaluate the dynamic operational risk in oil/gas and chemical industries, but also guides the process design and further optimization. To illustrate the probabilistic study, we present a case-study of a level control in an oil/gas separator at an offshore plant.

  11. 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.

  12. 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

  13. Vacuum ultraviolet beamline at the Swiss Light Source for chemical dynamics studies

    International Nuclear Information System (INIS)

    Johnson, Melanie; Bodi, Andras; Schulz, Lothar; Gerber, Thomas

    2009-01-01

    A bend-magnet vacuum ultraviolet (VUV) beamline, intended for chemical dynamics studies, was constructed and brought into operation at the Swiss Light Source (SLS) of the Paul Scherrer Institut. The beamline delivers synchrotron radiation in the 5-30 eV photon energy range with a photon flux of 10 11 photons/s at 10 eV and 10 12 photons/s at 20 eV with a resolving power of 2500. The resolving power increases to 10 4 at the cost of photon flux. An in-house designed rare gas filter is used to suppress higher harmonic radiation by a factor of >10 4 , yielding purely monochromatic light in the energy range of 5-21.6 eV. The filter is compact, easy to align, requires a total pumping power of less than 645 l/s and consumes only 3 normal l/h of filter gas. It is located at the end of the beamline, right in front of the experimental endstation. It is usually operated at a higher pressure than the endstation, which offers the additional benefit of protecting the beamline vacuum from sample contamination.

  14. 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.

  15. 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

    2016-01-01

    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. PMID:27091972

  16. Fractal sets generated by chemical reactions discrete chaotic dynamics

    International Nuclear Information System (INIS)

    Gontar, V.; Grechko, O.

    2007-01-01

    Fractal sets composed by the parameters values of difference equations derived from chemical reactions discrete chaotic dynamics (DCD) and corresponding to the sequences of symmetrical patterns were obtained in this work. Examples of fractal sets with the corresponding symmetrical patterns have been presented

  17. Quantum and classical studies of collisional excitation in H + CO and two other projects in theoretical chemical dynamics

    International Nuclear Information System (INIS)

    Geiger, L.C.

    1985-01-01

    This dissertation is a collection of four projects in theoretical chemical dynamics. In the first two projects collisional excitation in H + CO was studied using the quasiclassical trajectory method and the quantum infinite order sudden approximation (QIOS). Integral cross sections calculated using these methods were found to agree well with experimental and classical IOS results. The trajectory study was also used to examine the effects of potential energy surface features on the dynamics. Two surfaces were examined: a fitted surface based on ab initio points and a global ab initio surface. Next, the quasiclassical trajectory method was used to obtain cross sections and rate constants for O + H 2 → OH + H and analogous deuterium isotope reactions. The results using the Johnson and Winter surface agreed well with those of transition state theory (TST) and experiment, except for O + HD → OH + D. TST rate constants were calculated using an ab initio surface. These results were in poor agreement with calculations using the Johnson and Winter surface. A theory of action-angle variables for coupled oscillator systems was developed in the fourth project

  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. Energy price slump and policy response in the coal-chemical industry district : a case study of Ordos with a system dynamics model

    OpenAIRE

    Wang, Delu; Ma, Gang; Song, Xuefeng; Liu, Yun

    2017-01-01

    We employ system dynamics method towards a coal-chemical industry district economy evolution model, using coal industry, the coal-chemical industry, their downstream industries, and the manufacture-related service industry. Moreover, we construct energy price and policy response scenarios based on Ordos’ management experience. The results show that the energy price slump had a negative impact on the overall economic development of the coal-chemical industry district, despite promoting non-res...

  20. 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.

  1. 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.

  2. 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…

  3. Application of synchrotron radiation in chemical dynamics

    International Nuclear Information System (INIS)

    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

  4. 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.

  5. 1H NMR study of the solvent THF concerning their structural and dynamical properties in chemically Li-intercalated SWNT

    KAUST Repository

    Schmid, Marc R.; Goze-Bac, Christophe; Bouhrara, Mohamed; Saih, Youssef; Mehring, Michael; Abou-Hamad, Edy

    2011-01-01

    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.

  6. Automated chemical kinetic modeling via hybrid reactive molecular dynamics and quantum chemistry simulations.

    Science.gov (United States)

    Döntgen, Malte; Schmalz, Felix; Kopp, Wassja A; Kröger, Leif C; Leonhard, Kai

    2018-06-13

    An automated scheme for obtaining chemical kinetic models from scratch using reactive molecular dynamics and quantum chemistry simulations is presented. This methodology combines the phase space sampling of reactive molecular dynamics with the thermochemistry and kinetics prediction capabilities of quantum mechanics. This scheme provides the NASA polynomial and modified Arrhenius equation parameters for all species and reactions that are observed during the simulation and supplies them in the ChemKin format. The ab initio level of theory for predictions is easily exchangeable and the presently used G3MP2 level of theory is found to reliably reproduce hydrogen and methane oxidation thermochemistry and kinetics data. Chemical kinetic models obtained with this approach are ready-to-use for, e.g., ignition delay time simulations, as shown for hydrogen combustion. The presented extension of the ChemTraYzer approach can be used as a basis for methodologically advancing chemical kinetic modeling schemes and as a black-box approach to generate chemical kinetic models.

  7. Nuclear magnetic resonance in pulse radiolysis. Chemically induced dynamic nuclear polarization

    International Nuclear Information System (INIS)

    Trifunac, A.D.; Johnson, K.W.; Lowers, R.H.

    1976-01-01

    Nuclear magnetic resonance and chemically induced dynamic nuclear polarization (CIDNP) were applied to the study of pulse radiolysis. Samples were irradiated with a 3-MeV electron beam from the Argonne Van de Graaff accelerator in an EPR magnet (approximately 4000 G) which had axial holes for beam access. A fast flow system transferred the irradiated solution to the rotating 5-mm NMR sample tube. The NMR spectra of mixtures of sodium acetate and methanol were presented to demonstrate the features of the CIDNP in pulse radiolysis

  8. The use of dynamic capabilities to boost innovation in a Brazilian Chemical Company

    Directory of Open Access Journals (Sweden)

    Cristiane Froehlich

    Full Text Available Abstract Dynamic capabilities seek to explain how competitive advantages can be built in rapidly changing environments. This study aims to assess how the application of dynamic capabilities can contribute to the expansion of innovation capabilities. Data was collected on ten semi-structured interviews with executives from a chemical company, and analyzed using qualitative content analysis. Results indicate that the application of dynamic capabilities contributes to the development of innovation capabilities through the consolidation of the first dynamic capability (sensing, which fosters innovation. Sensing can be considered an organizational capability, resulting from the integration between organizational strategies and the innovation practices of the organization as a whole. This study brings the following contributions the need to include a new microfoundation in the sensing capability, which in this study is called ‘processes to manage innovation on a strategic level' and the need to adapt another microfoundation related to the sensing capability, called ‘processes oriented toward collaboration with suppliers to complement and stimulate innovations within the company'. It is suggested that these processes should be reassessed in terms of their potential to generate and complement organizational innovation.

  9. Molecular-dynamics study of amorphization by introduction of chemical disorder in crystalline NiZr2

    International Nuclear Information System (INIS)

    Massobrio, C.; Pontikis, V.; Martin, G.

    1990-01-01

    By means of constant-temperature, constant-pressure molecular dynamics, we investigate the crystal-to-amorphous transformation of the intermetallic alloy NiZr 2 resulting from the introduction of antisite defects. We constructed an n-body potential in the framework of the second-moment approximation of the tight-binding description of the electronic density of states. This modeling of the interatomic forces is successful in reproducing both static and thermodynamic properties of the real material. The imposition of chemical disorder quantified by the appropriate value of the long-range-order parameter, S, engenders a volume expansion followed by relaxation to a stationary state characterized by lower density and higher potential energy. The behavior of the pair distribution functions, g(r), reveals that amorphization takes place for values of S≤0.6, the corresponding volume expansion being of the order of 2%. Moreover the thermodynamic states obtained by chemical destabilization and rapid quenching from the liquid state are nearly identical. On the time scale of our simulations (10 -10 s), no detectable long-range diffusion of either species follows the introduction of chemical disorder. Some relevant features of the pair distribution functions (first and second peak positions, number of nearest neighbors) are in good agreement with those obtained experimentally from amorphous NiZr 2 samples generated by rapid quenching

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

    Directory of Open Access Journals (Sweden)

    Ferdinandus

    Full Text Available 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.

  11. 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.

  12. Dynamics and Control of Chemical Reactors-Selectively Surveyed

    DEFF Research Database (Denmark)

    Jørgensen, S. B.; Jensen, N.

    1989-01-01

    The chemical reactor or bioreactor is physically at a central position in a process, and often with a decisive role on the overall technical and economical performance. Even though application of feedback control on reactors is gaining momentum and on-line optimization has been implemented....... For bioreactors the theory and practice of reactor design, dynamics and control have to be adapted to the peculiarities of the biological catalysts. Enzymes, the protein catalysts, are the simplest ones, which have many common features with chemical catalysts. The living cells are much more complex, these growing...... in industry, many reactor control problems are still left unsolved or only partly solved using open loop strategies where disturbance rejection and model inaccuracies have to be handled through manual reactor control and feedback control of raw material preprocessing and product purification operations...

  13. 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.

  14. Intra- und intermolecular hydrogen bonds. Spectroscopic, quantum chemical and molecular dynamics studies

    International Nuclear Information System (INIS)

    Simperler, A.

    1999-03-01

    Intra- and intermolecular H-bonds have been investigated with spectroscopic, quantum chemical, and molecular dynamics methods. The work is divided into the following three parts: 1. Intramolecular interactions in ortho-substituted phenols. Theoretical and experimental data that characterizes the intramolecular hydrogen bonds in 48 different o-substituted phenols are discussed. The study covers various kinds of O-H ... Y -type interactions (Y= N, O, S, F, Cl, Br, I, C=C, C=-C, and C-=N). The bond strength sequences for several series of systematically related compounds as obtained from IR spectroscopy data (i.e., v(OH) stretching frequencies) are discussed and reproduced with several theoretical methods (B3LYP/6-31G(d,p), B3LYP/6-311G(d,p), B3LYP/6-31++G(d,p), B3LYP/DZVP, MP2/6-31G(d,p), and MP2/6-31++G(d,p) levels of theory). The experimentally determined sequences are interpreted in terms of the intrinsic properties of the molecules: hydrogen bond distances, Mulliken partial charges, van der Waals radii, and electron densities of the Y-proton acceptors. 2. Competitive hydrogen bonds and conformational equilibria in 2,6-disubstituted phenols containing two different carbonyl substituents. The rotational isomers of ten unsymmetrical 2,6-disubstituted phenols as obtained by combinations of five different carbonyl substituents (COOH, COOCH 3 , CHO, COCH 3 , and CONH 2 ) have been theoretically investigated at the B3LYP/6-31G(d,p) level of theory. The relative stability of four to five conformers of each compound were determined by full geometry optimization for free molecules as well as for molecules in reaction fields with dielectric constants up to ε=37.5. A comparison with IR spectroscopic data of available compounds revealed excellent agreement with the theoretically predicted stability sequences and conformational equilibria. The stability of a conformer could be interpreted to be governed by the following two contributions: (i) an attractive hydrogen bond

  15. Moessbauer spectroscopy-nuclear hyperfine technique for studying dynamic chemical states of iron complexes

    International Nuclear Information System (INIS)

    Maeda, Y.

    2005-01-01

    A brief introduction of Moessbauer spectroscopy will be presented, followed by a discussion of the Moessbauer parameters, isomer shifts, quadrupole splittings, and spectral shapes of complexes in the presence of relaxation of the electronic states of the iron atoms. The usefulness of Moessbauer spectroscopy to demonstrate the dynamic phenomena of electronic states will be discussed in this lecture. (1) The Moessbauer spectra of mixed valence dinuclear and trinuclear iron complexes will be discussed in connection with the chemical structure of the complexes: The values of the quadrupole splittings and isomer shifts of [Fe II Fe III (bpmp) (ppa) 2 ](BF 4 ) 2 increase on raising the temperature, where Hbpmp represents 2,6-bis[bis(2- pyridylmethyl)aminoethyl]-4-methylphenol and ppa is 3-n-phenylpropionic acid. The spectra can be accounted for by postulating intramolecular electron exchange between two energetically inequivalent vibronic states Fe A 2+ Fe B 3+ and Fe A 3+ Fe B 2+ : The apparent time averaged valence states of the iron atoms are 2.2 and 2.8 on the Moessbauer time scale at 293 K. (2) The Moessbauer spectra of iron(III) spin-crossover complexes will be discussed in connection with the spin-transition rate and chemical structure of the complexes. The Moessbauer spectra of spin-crossover iron(III) complexes with LIESST (Light Induced Electronic Spin-State Transition) and of metallomesogens will be discussed to illustrate the extension of this research area by the use of Moessbauer spectroscopy.

  16. Empirical Force Fields for Mechanistic Studies of Chemical Reactions in Proteins.

    Science.gov (United States)

    Das, A K; Meuwly, M

    2016-01-01

    Following chemical reactions in atomistic detail is one of the most challenging aspects of current computational approaches to chemistry. In this chapter the application of adiabatic reactive MD (ARMD) and its multistate version (MS-ARMD) are discussed. Both methods allow to study bond-breaking and bond-forming processes in chemical and biological processes. Particular emphasis is put on practical aspects for applying the methods to investigate the dynamics of chemical reactions. The chapter closes with an outlook of possible generalizations of the methods discussed. © 2016 Elsevier Inc. All rights reserved.

  17. ORIGIN OF CHEMICAL AND DYNAMICAL PROPERTIES OF THE GALACTIC THICK DISK

    International Nuclear Information System (INIS)

    Bekki, Kenji; Tsujimoto, Takuji

    2011-01-01

    We adopt a scenario in which the Galactic thick disk was formed by minor merging between the first generation of the Galactic thin disk (FGTD) and a dwarf galaxy about ∼9 Gyr ago and thereby investigate chemical and dynamical properties of the Galactic thick disk. In this scenario, the dynamical properties of the thick disk have long been influenced both by the mass growth of the second generation of the Galactic thin disk (i.e., the present thin disk) and by its non-axisymmetric structures. On the other hand, the early star formation history and chemical evolution of the thin disk was influenced by the remaining gas of the thick disk. Based on N-body simulations and chemical evolution models, we investigate the radial metallicity gradient, structural and kinematical properties, and detailed chemical abundance patterns of the thick disk. Our numerical simulations show that the ancient minor merger event can significantly flatten the original radial metallicity gradient of the FGTD, in particular, in the outer part, and also can be responsible for migration of inner metal-rich stars into the outer part (R > 10 kpc). The simulations show that the central region of the thick disk can develop a bar due to dynamical effects of a separate bar in the thin disk. Whether or not rotational velocities (V φ ) can correlate with metallicities ([Fe/H]) for the simulated thick disks depends on the initial metallicity gradients of the FGTDs. The simulated orbital eccentricity distributions in the thick disk for models with higher mass ratios (∼0.2) and lower orbital eccentricities (∼0.5) of minor mergers are in good agreement with the corresponding observations. The simulated V φ -|z| relation of the thick disk in models with low orbital inclination angles of mergers are also in good agreement with the latest observational results. The vertical metallicity gradient of the simulated thick disk is rather flat or very weakly negative in the solar neighborhood. Our Galactic

  18. Chemical kinetic insights into the ignition dynamics of n-hexane

    KAUST Repository

    Tingas, Alexandros

    2017-10-13

    Normal alkanes constitute a significant fraction of transportation fuels, and are the primary drivers of ignition processes in gasoline and diesel fuels. Low temperature ignition of n-alkanes is driven by a complex sequence of oxidation reactions, for which detailed mechanisms are still being developed. The current study explores the dynamics of low-temperature ignition of n-hexane/air mixtures, and identifies chemical pathways that characterize the combustion process. Two chemical kinetic mechanisms were selected as a comparative study in order to better understand the role of specific reaction sequences in ignition dynamics: one mechanism including a new third sequential O2 addition reaction pathways (recently proposed by Wang et al. 2017), while the other without (Zhang et al. 2015). The analysis is conducted by applying tools generated from the computational singular perturbation (CSP) approach to two distinct ignition phenomena: constant volume and compression ignition. In both cases, the role of the third sequential O2 addition reactions proves to be significant, although it is found to be much more pronounced in the constant volume cases compared to the HCCI. In particular, in the constant volume ignition case, reactions present in the third sequential O2 addition reaction pathways (e.g., KDHP  →  products + OH) contribute significantly to the explosivity of the mixture; when accounted for along with reactions P(OOH)2 + O2  →  OOP(OOH)2 and OOP(OOH)2  →  KDHP + OH, they decrease ignition delay time of the mixture by up to 40%. Under HCCI conditions, in the first-stage ignition, the third-O2 addition reactions contribute to the process, although their role decays with time and becomes negligible at the end of the first stage. The second ignition stage is dominated almost exclusively by hydrogen-related chemistry.

  19. 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.

  20. Disorder-induced amorphization of intermetallic compounds: A molecular dynamics study

    Energy Technology Data Exchange (ETDEWEB)

    Massobrio, C. (Ecole Polytechnique Federale, Lausanne (Switzerland). Inst. de Physique Experimentale); Pontikis, V.; Doan, N.V.; Martin, G. (CEA Centre d' Etudes Nucleaires de Saclay, 91 - Gif-sur-Yvette (France). Dept. de Physique des Particules Elementaires)

    The reaction of the crystalline compound NiZr{sub 2} to imposed chemical disorder has been studied by molecular dynamics in the isobaric canonical ensemble. The cohesive energy used is inspired by the second moment apporoximation of the local density of states in the tight binding model. Imposed chemical disorder induced swelling (3% for full disorder, 1% for 10% disorder). Above 10% disorder, the crystalline structure athermally collapses to an amorphous state which retains much of the local chemical order. (orig.).

  1. Disorder-induced amorphization of intermetallic compounds: A molecular dynamics study

    International Nuclear Information System (INIS)

    Massobrio, C.; Pontikis, V.; Doan, N.V.; Martin, G.

    1991-01-01

    The reaction of the crystalline compound NiZr 2 to imposed chemical disorder has been studied by molecular dynamics in the isobaric canonical ensemble. The cohesive energy used is inspired by the second moment apporoximation of the local density of states in the tight binding model. Imposed chemical disorder induced swelling (3% for full disorder, 1% for 10% disorder). Above 10% disorder, the crystalline structure athermally collapses to an amorphous state which retains much of the local chemical order. (orig.)

  2. Model study of the impacts of emissions, chemical and dynamical processes on the CO variability in the tropical upper troposphere and lower stratosphere

    Directory of Open Access Journals (Sweden)

    Chunxiao Wang

    2015-07-01

    Full Text Available The Whole Atmosphere Community Climate Model (WACCM is used to investigate the relative importance of CO emissions, chemical and dynamical processes on temporal variations of CO in the tropical upper troposphere (UT and the lower stratosphere (LS. The semi-annual oscillation (SAO in the tropical UT and the annual oscillation (AO in the tropical LS detected in the MLS CO observations can be well captured by the model. The model simulations reveal that the CO surface emissions explain most of the SAO signals in the tropical UT, with the remainder being attributed to dynamical and chemical processes. The CO AO in the LS primarily results from combined effects of dynamical and chemical processes while the dynamical and chemical processes make opposite contributions to the CO AO signals, consistent with the previous findings. Our analysis further reveals that CO surface emissions tend to weaken the amplitude of the CO annual cycle in the tropical LS, while the annual variations in the meridional component of the Brewer–Dobson (BD circulation can amplify the annual variations of CO above 30 hPa. The model simulations also indicate that the CO annual cycle in the LS has a mixed behaviour with the annual variations of tropical upwelling reflected in CO between ~70 and ~50 hPa and a standard tape-recorder signal above 50 hPa. Moreover, the AO signals of CO exist up to 10 hPa when the chemical processes are switched off. The temporal and spatial variations of CO in the UT and near the tropopause are mainly driven by the upward transport of CO by tropical deep convection and the Asian summer monsoon circulation. In the early stage of the South Asian summer monsoon over the Bay of Bengal and the South China in the late spring and early summer, the transport of the CO surface emissions over Southeast Asia by the South Asian summer monsoon leads to an increase in the tropical CO, but the horizontal transport from the extratropics into the tropics (termed in

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

    International Nuclear Information System (INIS)

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

    1978-01-01

    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

  4. The Role of Electronic Excitations on Chemical Reaction Dynamics at Metal, Semiconductor and Nanoparticle Surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Tully, John C. [Yale Univ., New Haven, CT (United States)

    2017-06-10

    Chemical reactions are often facilitated and steered when carried out on solid surfaces, essential for applications such as heterogeneous catalysis, solar energy conversion, corrosion, materials processing, and many others. A critical factor that can determine the rates and pathways of chemical reactions at surfaces is the efficiency and specificity of energy transfer; how fast does energy move around and where does it go? For reactions on insulator surfaces energy transfer generally moves in and out of vibrations of the adsorbed molecule and the underlying substrate. By contrast, on metal surfaces, metallic nanoparticles and semiconductors, another pathway for energy flow opens up, excitation and de-excitation of electrons. This so-called “nonadiabatic” mechanism often dominates the transfer of energy and can directly impact the course of a chemical reaction. Conventional computational methods such as molecular dynamics simulation do not account for this nonadiabatic behavior. The current DOE-BES funded project has focused on developing the underlying theoretical foundation and the computational methodology for the prediction of nonadiabatic chemical reaction dynamics at surfaces. The research has successfully opened up new methodology and new applications for molecular simulation. In particular, over the last three years, the “Electronic Friction” theory, pioneered by the PI, has now been developed into a stable and accurate computational method that is sufficiently practical to allow first principles “on-the-fly” simulation of chemical reaction dynamics at metal surfaces.

  5. Resonance Ionization Mass Spectrometry (RIMS): applications in spectroscopy and chemical dynamics

    International Nuclear Information System (INIS)

    Naik, P.D.; Kumar, Awadhesh; Upadhyaya, Hari; Bajaj, P.N.

    2009-01-01

    Resonance ionization is a photophysical process wherein electromagnetic radiation is used to ionize atoms, molecules, transient species, etc., by exciting them through their quantum states. The number of photons required to ionize depends on the species being investigated and energy of the photon. Once a charged particle is produced, it is easy to detect it with high efficiency. With the advent of narrow band high power pulsed and cw tunable dye lasers, it has blossomed into a powerful spectroscopic and analytical technique, commonly known as resonance ionization spectroscopy (RIS)/resonance enhanced multiphoton ionization (REMPI). The alliance of resonance ionization with mass spectrometry has grown into a still more powerful technique, known as resonance ionization mass spectrometry (RIMS), which has made significant contributions in a variety of frontier areas of research and development, such as spectroscopy, chemical dynamics, analytical chemistry, cluster science, surface science, radiochemistry, nuclear physics, biology, environmental science, material science, etc. In this article, we shall describe the application of resonance ionization mass spectrometry to spectroscopy of uranium and chemical dynamics of polyatomic molecules

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

    International Nuclear Information System (INIS)

    Tel, Tamas; Moura, Alessandro de; Grebogi, Celso; Karolyi, Gyoergy

    2005-01-01

    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

  7. 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.

  8. Molecular Dynamics Study of Thermally Augmented Nanodroplet Motion on Chemical Energy Induced Wettability Gradient Surfaces.

    Science.gov (United States)

    Chakraborty, Monojit; Chowdhury, Anamika; Bhusan, Richa; DasGupta, Sunando

    2015-10-20

    Droplet motion on a surface with chemical energy induced wettability gradient has been simulated using molecular dynamics (MD) simulation to highlight the underlying physics of molecular movement near the solid-liquid interface including the contact line friction. The simulations mimic experiments in a comprehensive manner wherein microsized droplets are propelled by the surface wettability gradient against forces opposed to motion. The liquid-wall Lennard-Jones interaction parameter and the substrate temperature are varied to explore their effects on the three-phase contact line friction coefficient. The contact line friction is observed to be a strong function of temperature at atomistic scales, confirming their experimentally observed inverse functionality. Additionally, the MD simulation results are successfully compared with those from an analytical model for self-propelled droplet motion on gradient surfaces.

  9. Initial Chemical Events in CL-20 Under Extreme Conditions: An Ab Initio Molecular Dynamics Study

    National Research Council Canada - National Science Library

    Isaev, Olexandr; Kholod, Yana; Gorb, Leonid; Qasim, Mohammad; Fredrickson, Herb; Leszczynski, Jerzy

    2006-01-01

    .... In the present study molecular structure, electrostatic potential, vibrational spectrum and dynamics of thermal decomposition of CL-20 have been investigated by static and dynamic methods of ab...

  10. Thermodiffusion as a means to manipulate liquid film dynamics on chemically patterned surfaces.

    Science.gov (United States)

    Kalpathy, Sreeram K; Shreyes, Amrita Ravi

    2017-06-07

    The model problem examined here is the stability of a thin liquid film consisting of two miscible components, resting on a chemically patterned solid substrate and heated from below. In addition to surface tension gradients, the temperature variations also induce gradients in the concentration of the film by virtue of thermodiffusion/Soret effects. We study the stability and dewetting behaviour due to the coupled interplay between thermal gradients, Soret effects, long-range van der Waals forces, and wettability gradient-driven flows. Linear stability analysis is first employed to predict growth rates and the critical Marangoni number for chemically homogeneous surfaces. Then, nonlinear simulations are performed to unravel the interfacial dynamics and possible locations of the film rupture on chemically patterned substrates. Results suggest that appropriate tuning of the Soret parameter and its direction, in conjunction with either heating or cooling, can help manipulate the location and time scales of the film rupture. The Soret effect can either potentially aid or oppose film instability depending on whether the thermal and solutal contributions to flow are cooperative or opposed to each other.

  11. Dynamics of chemical reactions of multiply-charged cations: Information from beam scattering experiments

    Czech Academy of Sciences Publication Activity Database

    Herman, Zdeněk

    2015-01-01

    Roč. 378, FEB 2015 (2015), s. 113-126 ISSN 1387-3806 Institutional support: RVO:61388955 Keywords : Multiply-charged ions * Dynamics of chemical reactions * Beam scattering Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.183, year: 2015

  12. 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.

  13. Recoil generated radiotracers in studies of molecular dynamics

    International Nuclear Information System (INIS)

    Spicer, L.D.

    1981-01-01

    This chapter summarizes many of the contributions that the recoil technique of generating excited radiotracer atoms in the presence of a thermal environment is making to the field of chemical dynamics. Specific topics discussed critically include characterization of the generation and behavior of excited molecules including fragmentation kinetics and energy transfer, measurement of thermal and hot kinetic parameters, and studies of reaction mechanisms and stereochemistry as a function of reaction energy. Distinctive features that provide unique approaches to dynamical problems are evaluated in detail and the complementarity with more conventional techniques is addressed. Prospects for future applications are also presented

  14. 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

  15. Energy price slump and policy response in the coal-chemical industry district: A case study of Ordos with a system dynamics model

    International Nuclear Information System (INIS)

    Wang, Delu; Ma, Gang; Song, Xuefeng; Liu, Yun

    2017-01-01

    We employ system dynamics method towards a coal-chemical industry district economy evolution model, using coal industry, the coal-chemical industry, their downstream industries, and the manufacture-related service industry. Moreover, we construct energy price and policy response scenarios based on Ordos’ management experience. The results show that the energy price slump had a negative impact on the overall economic development of the coal-chemical industry district, despite promoting non-resource industries. Furthermore, policies had different effects on the industry's output value and profit. In the long-term, developing alternative industries (AI) helps increase the industrial output value and profit. Decreasing value added tax (VAT) has immediate results and a distinctive effect on industrial short-term production value and profit, its long-term effect being limited. The effect of production limit (PL) on industrial profit is stronger than output value, and financial support (FS) is more conducive to improve the latter. However, coal mining and coal-chemical loan increases decrease the gross industrial profit level. Technology innovation (TI) has the best individual policy overall effect on production value and profits. Furthermore, the simultaneous implementation of PL, TI and AI can generate the synergy effect for each of them. And the simultaneous implementation of VAT and one or couple of other policies will generate the crowding-out effect both for VAT and other policies. - Highlights: • A system dynamics model of the coal-chemical industry district economy evolution in Ordos is constructed. • The impact of coal and oil prices slump on the output value and profit of each industry is revealed. • The differences in the effects especially cumulative effects of different response policies are clarified. • The crowding-out and synergy effects of policy implementation are analyzed.

  16. Experimental research of the impact of the dosing of chemical reagents on the dynamic behavior of regulation system of cycle chemistry

    Science.gov (United States)

    Yegoshina, O. V.; Bolshakova, N. A.

    2017-11-01

    Organization of reliable chemical control for maintaining cycle chemistry is one of the most important problems to be solved at the present time the design and operation of thermal power plants. To maintain optimal parameters of cycle chemistry are used automated chemical control system and regulation system of dosing chemical reagents. Reliability and stability analyzer readings largely determine the reliability of the water cycle chemistry. Now the most common reagents are ammonia, alkali and film-forming amines. In this paper are presented the results of studies of the impact of concentration and composition of chemical reagents for readings stability of automatic analyzers and transients time of control systems for cycles chemistry. Research of the impact of chemical reagents on the dynamic behavior of regulation system for cycle chemistry was conducted at the experimental facility of the Department of thermal power stations of the Moscow Engineering Institute. This experimental facility is model of the work of regulation system for cycle chemistry close to the actual conditions on the energy facilities CHP. Analysis of results of the impact of chemical reagent on the dynamic behavior of ammonia and film forming amines dosing systems showed that the film-forming amines dosing system is more inertia. This emphasizes the transition process of the system, in which a half times longer dosing of ammonia. Results of the study can be used to improve the monitoring systems of water chemical treatment.

  17. Study of spatially extended dynamical systems using probabilistic cellular automata

    International Nuclear Information System (INIS)

    Vanag, Vladimir K

    1999-01-01

    Spatially extended dynamical systems are ubiquitous and include such things as insect and animal populations; complex chemical, technological, and geochemical processes; humanity itself, and much more. It is clearly desirable to have a certain universal tool with which the highly complex behaviour of nonlinear dynamical systems can be analyzed and modelled. For this purpose, cellular automata seem to be good candidates. In the present review, emphasis is placed on the possibilities that various types of probabilistic cellular automata (PCA), such as DSMC (direct simulation Monte Carlo) and LGCA (lattice-gas cellular automata), offer. The methods are primarily designed for modelling spatially extended dynamical systems with inner fluctuations accounted for. For the Willamowskii-Roessler and Oregonator models, PCA applications to the following problems are illustrated: the effect of fluctuations on the dynamics of nonlinear systems; Turing structure formation; the effect of hydrodynamic modes on the behaviour of nonlinear chemical systems (stirring effects); bifurcation changes in the dynamical regimes of complex systems with restricted geometry or low spatial dimension; and the description of chemical systems in microemulsions. (reviews of topical problems)

  18. Spatiotemporal chaos in the dynamics of buoyantly and diffusively unstable chemical fronts

    Science.gov (United States)

    Baroni, M. P. M. A.; Guéron, E.; De Wit, A.

    2012-03-01

    Nonlinear dynamics resulting from the interplay between diffusive and buoyancy-driven Rayleigh-Taylor (RT) instabilities of autocatalytic traveling fronts are analyzed numerically for various values of the relevant parameters. These are the Rayleigh numbers of the reactant A and autocatalytic product B solutions as well as the ratio D =DB/DA between the diffusion coefficients of the two key chemical species. The interplay between the coarsening dynamics characteristic of the RT instability and the constant short wavelength modulation of the diffusive instability can lead in some regimes to complex dynamics dominated by irregular succession of birth and death of fingers. By using spectral entropy measurements, we characterize the transition between order and spatial disorder in this system. The analysis of the power spectrum and autocorrelation function, moreover, identifies similarities between the various spatial patterns. The contribution of the diffusive instability to the complex dynamics is discussed.

  19. 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.

  20. Studies in chemical dynamics

    International Nuclear Information System (INIS)

    Kuppermann, A.

    1978-01-01

    Progress made in the following studies is reported: low-energy electron scattering; variable-angle photoelectron spectroscopy; laser photochemistry and spectroscopy; and collisions in crossed molecular beams

  1. Direct single-molecule dynamic detection of chemical reactions.

    Science.gov (United States)

    Guan, Jianxin; Jia, Chuancheng; Li, Yanwei; Liu, Zitong; Wang, Jinying; Yang, Zhongyue; Gu, Chunhui; Su, Dingkai; Houk, Kendall N; Zhang, Deqing; Guo, Xuefeng

    2018-02-01

    Single-molecule detection can reveal time trajectories and reaction pathways of individual intermediates/transition states in chemical reactions and biological processes, which is of fundamental importance to elucidate their intrinsic mechanisms. We present a reliable, label-free single-molecule approach that allows us to directly explore the dynamic process of basic chemical reactions at the single-event level by using stable graphene-molecule single-molecule junctions. These junctions are constructed by covalently connecting a single molecule with a 9-fluorenone center to nanogapped graphene electrodes. For the first time, real-time single-molecule electrical measurements unambiguously show reproducible large-amplitude two-level fluctuations that are highly dependent on solvent environments in a nucleophilic addition reaction of hydroxylamine to a carbonyl group. Both theoretical simulations and ensemble experiments prove that this observation originates from the reversible transition between the reactant and a new intermediate state within a time scale of a few microseconds. These investigations open up a new route that is able to be immediately applied to probe fast single-molecule physics or biophysics with high time resolution, making an important contribution to broad fields beyond reaction chemistry.

  2. Role of aromatic amino acids in carbohydrate binding of plant lectins : Laser photo chemically induced dynamic nuclear polarization study of hevein domain-containing lectins

    NARCIS (Netherlands)

    Siebert, HC; vonderLieth, CW; Kaptein, R; Beintema, JJ; Dijkstra, K; vanNuland, N; Soedjanaatmadja, UMS; Rice, A; Vliegenthart, JFG; Wright, CS; Gabius, HJ

    Carbohydrate recognition by lectins often involves the side chains of tyrosine, tryptophan, and histidine residues. These moieties are able to produce chemically induced dynamic nuclear polarization (CIDNP) signals after laser irradiation in the presence of a suitable radical pair-generating dye.

  3. Personal Chemical Exposure informatics

    Science.gov (United States)

    Chemical Exposure science is the study of human contact with chemicals (from manufacturing facilities, everyday products, waste) occurring in their environments and advances knowledge of the mechanisms and dynamics of events that cause or prevent adverse health outcomes. (adapted...

  4. Chemical elements dynamic in the fermentation process of ethanol producing

    International Nuclear Information System (INIS)

    Nepomuceno, N.; Nadai Fernandes, E.A. de; Bacchi, M.A.

    1994-01-01

    This paper provides useful information about the dynamics of chemical elements analysed by instrumental neutron activation analysis (INAA) and, found in the various segments of the fermentation process of producing ethanol from sugar cane. For this, a mass balance of Ce, Co, Cs, Eu, Fe, Hf, La, Sc, Sm, and Th, terrigenous elements, as well as Br, K, Rb, and Zn, sugar cane plant elements, has been demonstrated for the fermentation vats in industrial conditions of ethanol production. (author). 10 refs, 4 figs, 1 tab

  5. 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.

  6. Single-collision studies of hot atom energy transfer and chemical reaction

    International Nuclear Information System (INIS)

    Valentini, J.J.

    1991-01-01

    This report discusses research in the collision dynamics of translationally hot atoms, with funding with DOE for the project ''Single-Collision Studies of Hot Atom Energy Transfer and Chemical Reaction,'' Grant Number DE-FG03-85ER13453. The work reported here was done during the period September 9, 1988 through October 31, 1991. During this period this DOE-funded work has been focused on several different efforts: (1) experimental studies of the state-to-state dynamics of the H + RH → H 2 R reactions where RH is CH 4 , C 2 H 6 , or C 3 H 8 , (2) theoretical (quasiclassical trajectory) studies of hot hydrogen atom collision dynamics, (3) the development of photochemical sources of translationally hot molecular free radicals and characterization of the high resolution CARS spectroscopy of molecular free radicals, (4) the implementation of stimulated Raman excitation (SRE) techniques for the preparation of vibrationally state-selected molecular reactants

  7. Modelling of Mass Transfer Phenomena in Chemical and Biochemical Reactor Systems using Computational Fluid Dynamics

    DEFF Research Database (Denmark)

    Larsson, Hilde Kristina

    the velocity and pressure distributions in a fluid. CFD also enables the modelling of several fluids simultaneously, e.g. gas bubbles in a liquid, as well as the presence of turbulence and dissolved chemicals in a fluid, and many other phenomena. This makes CFD an appreciated tool for studying flow structures......, mixing, and other mass transfer phenomena in chemical and biochemical reactor systems. In this project, four selected case studies are investigated in order to explore the capabilities of CFD. The selected cases are a 1 ml stirred microbioreactor, an 8 ml magnetically stirred reactor, a Rushton impeller...... and an ion-exchange reaction are also modelled and compared to experimental data. The thesis includes a comprehensive overview of the fundamentals behind a CFD software, as well as a more detailed review of the fluid dynamic phenomena investigated in this project. The momentum and continuity equations...

  8. Chemical Industry Bandwidth Study

    Energy Technology Data Exchange (ETDEWEB)

    none,

    2006-12-01

    The Chemical Bandwidth Study provides a snapshot of potentially recoverable energy losses during chemical manufacturing. The advantage of this study is the use of "exergy" analysis as a tool for pinpointing inefficiencies.

  9. Characterization of electron-deficient chemical bonding of diborane with attosecond electron wavepacket dynamics and laser response

    International Nuclear Information System (INIS)

    Yonehara, Takehiro; Takatsuka, Kazuo

    2009-01-01

    We report a theoretical study of non-adiabatic electrons-nuclei coupled dynamics of diborane H 2 BH 2 BH 2 under several types of short pulse lasers. This molecule is known to have particularly interesting geometrical and electronic structures, which originate from the electron-deficient chemical bondings. We revisit the chemical bonding of diborane from the view point of electron wavepacket dynamics coupled with nuclear motions, and attempt to probe the characteristics of it by examining its response to intense laser fields. We study in the following three aspects, (i) bond formation of diborane by collision between two monoboranes, (ii) attosecond electron wavepacket dynamics in the ground state and first excited state by circularly polarized laser pulse, and (iii) induced fragmentation back to monoborane molecules by linearly polarized laser. The wave lengths of two types of laser field employed are 200 nm (in UV range) and 800 nm (in IR range), and we track the dynamics from hundreds of attoseconds up to few tens of femtoseconds. To this end, we apply the ab initio semiclassical Ehrenfest theory, into which the classical vector potential of a laser field is introduced. Basic features of the non-adiabatic response of electrons to the laser fields is elucidated in this scheme. To analyze the electronic wavepackets thus obtained, we figure out bond order density that is a spatial distribution of the bond order and bond order flux density arising only from the bonding regions, and so on. Main findings in this work are: (i) dimerization of monoboranes to diborane is so efficient that even intense laser is hard to prevent it; (ii) collective motions of electron flux emerge in the central BHHB bonding area in response to the circularly polarized laser fields; (iii) laser polarization with the direction of central two BH bonding vector is efficient for the cleavage of BH 3 -BH 3 ; and (iv) nuclear derivative coupling plays a critical role in the field induced

  10. A phenomenological approach to modeling chemical dynamics in nonlinear and two-dimensional spectroscopy.

    Science.gov (United States)

    Ramasesha, Krupa; De Marco, Luigi; Horning, Andrew D; Mandal, Aritra; Tokmakoff, Andrei

    2012-04-07

    We present an approach for calculating nonlinear spectroscopic observables, which overcomes the approximations inherent to current phenomenological models without requiring the computational cost of performing molecular dynamics simulations. The trajectory mapping method uses the semi-classical approximation to linear and nonlinear response functions, and calculates spectra from trajectories of the system's transition frequencies and transition dipole moments. It rests on identifying dynamical variables important to the problem, treating the dynamics of these variables stochastically, and then generating correlated trajectories of spectroscopic quantities by mapping from the dynamical variables. This approach allows one to describe non-Gaussian dynamics, correlated dynamics between variables of the system, and nonlinear relationships between spectroscopic variables of the system and the bath such as non-Condon effects. We illustrate the approach by applying it to three examples that are often not adequately treated by existing analytical models--the non-Condon effect in the nonlinear infrared spectra of water, non-Gaussian dynamics inherent to strongly hydrogen bonded systems, and chemical exchange processes in barrier crossing reactions. The methods described are generally applicable to nonlinear spectroscopy throughout the optical, infrared and terahertz regions.

  11. Emergency material allocation with time-varying supply-demand based on dynamic optimization method for river chemical spills.

    Science.gov (United States)

    Liu, Jie; Guo, Liang; Jiang, Jiping; Jiang, Dexun; Wang, Peng

    2018-04-13

    Aiming to minimize the damage caused by river chemical spills, efficient emergency material allocation is critical for an actual emergency rescue decision-making in a quick response. In this study, an emergency material allocation framework based on time-varying supply-demand constraint is developed to allocate emergency material, minimize the emergency response time, and satisfy the dynamic emergency material requirements in post-accident phases dealing with river chemical spills. In this study, the theoretically critical emergency response time is firstly obtained for the emergency material allocation system to select a series of appropriate emergency material warehouses as potential supportive centers. Then, an enumeration method is applied to identify the practically critical emergency response time, the optimum emergency material allocation and replenishment scheme. Finally, the developed framework is applied to a computational experiment based on south-to-north water transfer project in China. The results illustrate that the proposed methodology is a simple and flexible tool for appropriately allocating emergency material to satisfy time-dynamic demands during emergency decision-making. Therefore, the decision-makers can identify an appropriate emergency material allocation scheme in a balance between time-effective and cost-effective objectives under the different emergency pollution conditions.

  12. 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. © 2015 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.

  13. 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

  14. Quantum chemical molecular dynamical investigation of alkyl nitrite photo-dissociated on copper surfaces

    International Nuclear Information System (INIS)

    Wang Xiaojing; Wang Wei; Han Peilin; Kubo, Momoji; Miyamoto, Akira

    2008-01-01

    An accelerated quantum chemical molecular dynamical code 'Colors-Excite' was used to investigate the photolysis of alkyl nitrites series, RONO (R=CH 3 and C(CH 3 ) 3 ) on copper surfaces. Our calculations showed that the photo-dissociated processes are associated with the alkyl substituents of RONO when adsorbed on copper surfaces. For R=CH 3 , a two-step photolysis reaction occurred, yielding diverse intermediate products including RO radical, NO, and HNO, consistent with those reported in gas phase. While for R=C(CH 3 ) 3 , only one-step photolysis reaction occurred and gave intermediate products of RO radical and NO. Consequently, pure RO species were achieved to adsorb on metal surfaces by removing the NO species in photolysis reaction. The detailed photo-dissociated behaviors of RONO on copper surfaces with different alkyl substituents which are uncovered by the present simulation can be extended to explain the diverse dissociative mechanism experimentally observed. The quantum chemical molecular dynamical code 'Colors-Excite' is proved to be highly applicable to the photo-dissociations on metal surfaces

  15. High resolution time-of-flight spectrometer for crossed molecular beam study of elementary chemical reactions

    International Nuclear Information System (INIS)

    Qiu Minghui; Che Li; Ren Zefeng; Dai Dongxu; Wang Xiuyan; Yang Xueming

    2005-01-01

    In this article, we describe an apparatus in our laboratory for investigating elementary chemical reactions using the high resolution time-of-flight Rydberg tagging method. In this apparatus, we have adopted a rotating source design so that collision energy can be changed for crossed beam studies of chemical reactions. Preliminary results on the HI photodissociation and the F atom reaction with H 2 are reported here. These results suggest that the experimental apparatus is potentially a powerful tool for investigating state-to-state dynamics of elementary chemical reactions

  16. 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.

  17. Study on flow characteristics of chemically reacting liquid jet

    International Nuclear Information System (INIS)

    Hong Seon Dae; Okamoto, Koji; Takata, Takashi; Yamaguchi, Akira

    2004-07-01

    Tube rupture accidents in steam generators of sodium-cooled fast breeder reactors are important for safety because the rupture may propagates to neighboring tubes due to sodium-water reaction. In order to clarify the thermal-hydraulic phenomena in the accidents, the flow pattern and the interface in multi-phase flow must be investigated. The JNC cooperative research scheme on the nuclear fuel cycle with the University of Tokyo has been carried to develop a simultaneous measurement system of concentration and velocity profiles and to evaluate influence of chemical reaction on mixing phenomena. In the experiments, aqueous liquor of acetic acid and ammonium hydroxide are selected as a simulant fluid instead of liquid sodium and water vapor. The following conclusions are obtained in this research. Laser Induced Fluorescence (LIF) technique was adopted to measure reacting zone and pH distribution in chemically reacting liquid round free jet. As a result, it was found that the chemical reaction, which took place at the interface between the jet and outer flow, suppressed the mixing phenomenon (in 2001 research). Dynamic Particle Image Velocimetry (PIV) method was developed to measure instantaneous velocity profile with high temporal resolution. In the Dynamic PIV, a high-speed video camera coupled with a high-speed laser pulse generator was implemented. A time-line trend of interfacial area in the free jet was investigated with the Dynamic PIV. This technique was also applied to a complicated geometry (in 2002 research). A new algorithms for image analysis was developed to evaluated the Dynamic PIV data in detail. The characteristics of the mixing phenomenon with reacting jet such as the turbulent kinetic energy and the Reynolds stress were estimated in a spatial and temporal spectrum (in 2003 research). (author)

  18. Dynamics-based selective 2D 1H/1H chemical shift correlation spectroscopy under ultrafast MAS conditions

    Science.gov (United States)

    Zhang, Rongchun; Ramamoorthy, Ayyalusamy

    2015-05-01

    Dynamics plays important roles in determining the physical, chemical, and functional properties of a variety of chemical and biological materials. However, a material (such as a polymer) generally has mobile and rigid regions in order to have high strength and toughness at the same time. Therefore, it is difficult to measure the role of mobile phase without being affected by the rigid components. Herein, we propose a highly sensitive solid-state NMR approach that utilizes a dipolar-coupling based filter (composed of 12 equally spaced 90° RF pulses) to selectively measure the correlation of 1H chemical shifts from the mobile regions of a material. It is interesting to find that the rotor-synchronized dipolar filter strength decreases with increasing inter-pulse delay between the 90° pulses, whereas the dipolar filter strength increases with increasing inter-pulse delay under static conditions. In this study, we also demonstrate the unique advantages of proton-detection under ultrafast magic-angle-spinning conditions to enhance the spectral resolution and sensitivity for studies on small molecules as well as multi-phase polymers. Our results further demonstrate the use of finite-pulse radio-frequency driven recoupling pulse sequence to efficiently recouple weak proton-proton dipolar couplings in the dynamic regions of a molecule and to facilitate the fast acquisition of 1H/1H correlation spectrum compared to the traditional 2D NOESY (Nuclear Overhauser effect spectroscopy) experiment. We believe that the proposed approach is beneficial to study mobile components in multi-phase systems, such as block copolymers, polymer blends, nanocomposites, heterogeneous amyloid mixture of oligomers and fibers, and other materials.

  19. Dynamics-based selective 2D 1H/1H chemical shift correlation spectroscopy under ultrafast MAS conditions

    International Nuclear Information System (INIS)

    Zhang, Rongchun; Ramamoorthy, Ayyalusamy

    2015-01-01

    Dynamics plays important roles in determining the physical, chemical, and functional properties of a variety of chemical and biological materials. However, a material (such as a polymer) generally has mobile and rigid regions in order to have high strength and toughness at the same time. Therefore, it is difficult to measure the role of mobile phase without being affected by the rigid components. Herein, we propose a highly sensitive solid-state NMR approach that utilizes a dipolar-coupling based filter (composed of 12 equally spaced 90° RF pulses) to selectively measure the correlation of 1 H chemical shifts from the mobile regions of a material. It is interesting to find that the rotor-synchronized dipolar filter strength decreases with increasing inter-pulse delay between the 90° pulses, whereas the dipolar filter strength increases with increasing inter-pulse delay under static conditions. In this study, we also demonstrate the unique advantages of proton-detection under ultrafast magic-angle-spinning conditions to enhance the spectral resolution and sensitivity for studies on small molecules as well as multi-phase polymers. Our results further demonstrate the use of finite-pulse radio-frequency driven recoupling pulse sequence to efficiently recouple weak proton-proton dipolar couplings in the dynamic regions of a molecule and to facilitate the fast acquisition of 1 H/ 1 H correlation spectrum compared to the traditional 2D NOESY (Nuclear Overhauser effect spectroscopy) experiment. We believe that the proposed approach is beneficial to study mobile components in multi-phase systems, such as block copolymers, polymer blends, nanocomposites, heterogeneous amyloid mixture of oligomers and fibers, and other materials

  20. Study of virgin olive oil clarification by settling under dynamic conditions.

    Science.gov (United States)

    Gila, Abraham; Bejaoui, Mohamed Aymen; Beltrán, Gabriel; Aguilera, María Paz; Jiménez, Antonio

    2018-04-16

    Vertical centrifugation is the main method for virgin olive oil (VOO) clarification. However, in recent years, settling tanks are also being used to clarify the oils from decanters. They can operate under static or dynamic conditions. In this work, vertical centrifugation and settling under dynamic conditions for VOO clarification and their effects on VOO characteristics were compared. VOO quality parameters were not affected by the clarification systems studied. The vertical centrifugal separator (VCS) showed higher clarification efficiency, giving clarified oils with higher phenol content and better sensory characteristics. VOOs clarified by dynamic settling showed notable losses of phenols and worse sensory characteristics, since the tank purge system was not efficient, with most of the impurities remaining in the tanks. The VCS with minimal water addition is a quick operation with low water consumption and is a better option to produce VOOs of improved quality, especially in terms of longer shelf life and preservation of positive sensory notes. © 2018 Society of Chemical Industry. © 2018 Society of Chemical Industry.

  1. Effects of N-glycosylation on protein conformation and dynamics: Protein Data Bank analysis and molecular dynamics simulation study.

    Science.gov (United States)

    Lee, Hui Sun; Qi, Yifei; Im, Wonpil

    2015-03-09

    N-linked glycosylation is one of the most important, chemically complex, and ubiquitous post-translational modifications in all eukaryotes. The N-glycans that are covalently linked to proteins are involved in numerous biological processes. There is considerable interest in developments of general approaches to predict the structural consequences of site-specific glycosylation and to understand how these effects can be exploited in protein design with advantageous properties. In this study, the impacts of N-glycans on protein structure and dynamics are systematically investigated using an integrated computational approach of the Protein Data Bank structure analysis and atomistic molecular dynamics simulations of glycosylated and deglycosylated proteins. Our study reveals that N-glycosylation does not induce significant changes in protein structure, but decreases protein dynamics, likely leading to an increase in protein stability. Overall, these results suggest not only a common role of glycosylation in proteins, but also a need for certain proteins to be properly glycosylated to gain their intrinsic dynamic properties.

  2. Water dynamics of Ser-His-Glu-Cys-Asn powder and effects of moisture absorption on its chemical properties.

    Science.gov (United States)

    Lin, Songyi; Xue, Peiyu; Yang, Shuailing; Li, Xingfang; Dong, Xiuping; Chen, Feng

    2017-08-01

    This study has elucidated moisture dynamics in the soybean peptide, Ser-His-Glu-Cys-Asn (SHECN) powder by using dynamic vapor sorption (DVS) and nuclear magnetic resonance (NMR). We also tried to investigate the effects of moisture absorption on the biological activity and chemical properties of SHECN with some effective methods such as mid-infrared (MIR) spectroscopy and gas chromatography-mass spectrometry (GC-MS). DVS results showed that the moisture absorption of SHECN could reach a maximum of 33%, and the SHECN powder after synthesis actually existed in a trihydrate state of SHECN.3H 2 O. Low-field NMR revealed that three water proportions including strong combined water, binding water and bulk water were involved in SHECN moisture absorption and absored water dominantly existed in the form of combined water. Magnetic resonance imaging (MRI) and MIR spectroscopy results indicated that moisture absorption could change the morphology and structure of SHECN. After moisture absorption at 50% and 75% relative humidity, 19 volatiles were identified by GC-MS analysis. Additionally, this study showed that a part of reductive groups in SHECN was oxidized and its antioxidant ability declined significantly (P moisture absorption. Water absorbed into SHECN powder can significantly change its microstructure and cause its activity to decrease. We must prevent SHECN from absorbing moisture during storage because the water can accelerate the oxidation of samples and promote microbial reactions. © 2016 Society of Chemical Industry. © 2016 Society of Chemical Industry.

  3. Three-Dimensional Optical Trapping for Cell Isolation Using Tapered Fiber Probe by Dynamic Chemical Etching

    International Nuclear Information System (INIS)

    Taguchi, K; Okada, J; Nomura, Y; Tamura, K

    2012-01-01

    In this paper, chemically etched fiber probe was proposed for laser trapping and manipulation of cells. We fabricated tapered fiber probe by dynamic chemical etching technique. Three-Dimensional optical trap of a yeast cell dispersed in water solution could be formed by the fiber tip with 17deg tip. Optical forces were sufficient to move the yeast cell for trapping and manipulation. From these experimental results, it was found that our proposed tapered fiber tip was a promising tool for cell isolation.

  4. Dynamics of shearing force and its correlations with chemical compositions and dry matter digestibility of stylo ( stem

    Directory of Open Access Journals (Sweden)

    Xuejuan Zi

    2017-12-01

    Full Text Available Objective The study explored the dynamics of shearing force and its correlation with chemical compositions and in vitro dry matter digestibility (IVDMD of stylo. Methods The shearing force, diameter, linear density, chemical composition, and IVDMD of different height stylo stem were investigated. Linear regression analysis was done to determine the relationships between the shearing force and cut height, diameter, chemical composition, or IVDMD. Results The results showed that shearing force of stylo stem increased with plant height increasing and the crude protein (CP content and IVDMD decreased but fiber content increased over time, resulting in decreased forage value. In addition, tall stem had greater shearing force than short stem. Moreover, shearing force is positively correlated with stem diameter, linear density and fiber fraction, but negatively correlated with CP content and IVDMD. Conclusion Overall, shearing force is an indicator more direct, easier and faster to measure than chemical composition and digestibility for evaluation of forage nutritive value related to animal performance. Therefore, it can be used to evaluate the nutritive value of stylo.

  5. 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.

  6. Computer simulation of chemical nucleation

    International Nuclear Information System (INIS)

    Turner, J.S.

    1979-01-01

    The problem of nucleation at chemical instabilities is investigated by means of microscopic computer simulation. The first-order transition of interest involves a new kind of nucleation arising from chemical transformations rather than physical forces. Here it is the chemical state of matter, and not matter itself, which is spatially localized to form the nucleus for transition between different chemical states. First, the concepts of chemical instability, nonequilibrium phase transition, and dissipative structure are reviewed briefly. Then recently developed methods of reactive molecular dynamics are used to study chemical nucleation in a simple model chemical reactions. Finally, the connection of these studies to nucleation and condensation processes involving physical and chemical interactions is explored. (orig.)

  7. 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.

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

    KAUST Repository

    Do, Khanh; Risko, Chad; Anthony, John E; Amassian, Aram; Bredas, Jean-Luc

    2015-01-01

    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.

  9. Real-time nonlinear feedback control of pattern formation in (bio)chemical reaction-diffusion processes: a model study.

    Science.gov (United States)

    Brandt-Pollmann, U; Lebiedz, D; Diehl, M; Sager, S; Schlöder, J

    2005-09-01

    Theoretical and experimental studies related to manipulation of pattern formation in self-organizing reaction-diffusion processes by appropriate control stimuli become increasingly important both in chemical engineering and cellular biochemistry. In a model study, we demonstrate here exemplarily the application of an efficient nonlinear model predictive control (NMPC) algorithm to real-time optimal feedback control of pattern formation in a bacterial chemotaxis system modeled by nonlinear partial differential equations. The corresponding drift-diffusion model type is representative for many (bio)chemical systems involving nonlinear reaction dynamics and nonlinear diffusion. We show how the computed optimal feedback control strategy exploits the system inherent physical property of wave propagation to achieve desired control aims. We discuss various applications of our approach to optimal control of spatiotemporal dynamics.

  10. Some Sensitivity Studies of Chemical Transport Simulated in Models of the Soil-Plant-Litter System

    Energy Technology Data Exchange (ETDEWEB)

    Begovich, C.L.

    2002-10-28

    Fifteen parameters in a set of five coupled models describing carbon, water, and chemical dynamics in the soil-plant-litter system were varied in a sensitivity analysis of model response. Results are presented for chemical distribution in the components of soil, plants, and litter along with selected responses of biomass, internal chemical transport (xylem and phloem pathways), and chemical uptake. Response and sensitivity coefficients are presented for up to 102 model outputs in an appendix. Two soil properties (chemical distribution coefficient and chemical solubility) and three plant properties (leaf chemical permeability, cuticle thickness, and root chemical conductivity) had the greatest influence on chemical transport in the soil-plant-litter system under the conditions examined. Pollutant gas uptake (SO{sub 2}) increased with change in plant properties that increased plant growth. Heavy metal dynamics in litter responded to plant properties (phloem resistance, respiration characteristics) which induced changes in the chemical cycling to the litter system. Some of the SO{sub 2} and heavy metal responses were not expected but became apparent through the modeling analysis.

  11. Detailed balance method for chemical potential determination in Monte Carlo and molecular dynamics simulations

    International Nuclear Information System (INIS)

    Fay, P.J.; Ray, J.R.; Wolf, R.J.

    1994-01-01

    We present a new, nondestructive, method for determining chemical potentials in Monte Carlo and molecular dynamics simulations. The method estimates a value for the chemical potential such that one has a balance between fictitious successful creation and destruction trials in which the Monte Carlo method is used to determine success or failure of the creation/destruction attempts; we thus call the method a detailed balance method. The method allows one to obtain estimates of the chemical potential for a given species in any closed ensemble simulation; the closed ensemble is paired with a ''natural'' open ensemble for the purpose of obtaining creation and destruction probabilities. We present results for the Lennard-Jones system and also for an embedded atom model of liquid palladium, and compare to previous results in the literature for these two systems. We are able to obtain an accurate estimate of the chemical potential for the Lennard-Jones system at higher densities than reported in the literature

  12. Model reduction of multiscale chemical langevin equations: a numerical case study.

    Science.gov (United States)

    Sotiropoulos, Vassilios; Contou-Carrere, Marie-Nathalie; Daoutidis, Prodromos; Kaznessis, Yiannis N

    2009-01-01

    Two very important characteristics of biological reaction networks need to be considered carefully when modeling these systems. First, models must account for the inherent probabilistic nature of systems far from the thermodynamic limit. Often, biological systems cannot be modeled with traditional continuous-deterministic models. Second, models must take into consideration the disparate spectrum of time scales observed in biological phenomena, such as slow transcription events and fast dimerization reactions. In the last decade, significant efforts have been expended on the development of stochastic chemical kinetics models to capture the dynamics of biomolecular systems, and on the development of robust multiscale algorithms, able to handle stiffness. In this paper, the focus is on the dynamics of reaction sets governed by stiff chemical Langevin equations, i.e., stiff stochastic differential equations. These are particularly challenging systems to model, requiring prohibitively small integration step sizes. We describe and illustrate the application of a semianalytical reduction framework for chemical Langevin equations that results in significant gains in computational cost.

  13. Dynamical interactions between solute and solvent studied by nonlinear infrared spectroscopy

    International Nuclear Information System (INIS)

    Ohta, K.; Tominaga, K.

    2006-01-01

    Interactions between solute and solvent play an important role in chemical reaction dynamics and in many relaxation processes in condensed phases. Recently third-order nonlinear infrared (IR) spectroscopy has shown to be useful to investigate solute-solvent interaction and dynamics of the vibrational transition. These studies provide detailed information on the energy relaxation of the vibrationally excited state, and the time scale and the magnitude of the time correlation functions of the vibrational frequency fluctuations. In this work we have studied vibrational energy relaxation (VER) of solutions and molecular complexes by nonlinear IR spectroscopy, especially IR pump-probe method, to understand the microscopic interactions in liquids. (authors)

  14. Modeling dynamics of biological and chemical components of aquatic ecosystems

    International Nuclear Information System (INIS)

    Lassiter, R.R.

    1975-05-01

    To provide capability to model aquatic ecosystems or their subsystems as needed for particular research goals, a modeling strategy was developed. Submodels of several processes common to aquatic ecosystems were developed or adapted from previously existing ones. Included are submodels for photosynthesis as a function of light and depth, biological growth rates as a function of temperature, dynamic chemical equilibrium, feeding and growth, and various types of losses to biological populations. These submodels may be used as modules in the construction of models of subsystems or ecosystems. A preliminary model for the nitrogen cycle subsystem was developed using the modeling strategy and applicable submodels. (U.S.)

  15. Radiation-Induced Chemical Dynamics in Ar Clusters Exposed to Strong X-Ray Pulses

    Science.gov (United States)

    Kumagai, Yoshiaki; Jurek, Zoltan; Xu, Weiqing; Fukuzawa, Hironobu; Motomura, Koji; Iablonskyi, Denys; Nagaya, Kiyonobu; Wada, Shin-ichi; Mondal, Subhendu; Tachibana, Tetsuya; Ito, Yuta; Sakai, Tsukasa; Matsunami, Kenji; Nishiyama, Toshiyuki; Umemoto, Takayuki; Nicolas, Christophe; Miron, Catalin; Togashi, Tadashi; Ogawa, Kanade; Owada, Shigeki; Tono, Kensuke; Yabashi, Makina; Son, Sang-Kil; Ziaja, Beata; Santra, Robin; Ueda, Kiyoshi

    2018-06-01

    We show that electron and ion spectroscopy reveals the details of the oligomer formation in Ar clusters exposed to an x-ray free electron laser (XFEL) pulse, i.e., chemical dynamics triggered by x rays. With guidance from a dedicated molecular dynamics simulation tool, we find that van der Waals bonding, the oligomer formation mechanism, and charge transfer among the cluster constituents significantly affect ionization dynamics induced by an XFEL pulse of moderate fluence. Our results clearly demonstrate that XFEL pulses can be used not only to "damage and destroy" molecular assemblies but also to modify and transform their molecular structure. The accuracy of the predictions obtained makes it possible to apply the cluster spectroscopy, in connection with the respective simulations, for estimation of the XFEL pulse fluence in the fluence regime below single-atom multiple-photon absorption, which is hardly accessible with other diagnostic tools.

  16. 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.

  17. 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.

  18. Action-Derived Molecular Dynamics in the Study of Rare Events

    Energy Technology Data Exchange (ETDEWEB)

    Passerone, Daniele; Parrinello, Michele

    2001-09-03

    We present a practical method to generate classical trajectories with fixed initial and final boundary conditions. Our method is based on the minimization of a suitably defined discretized action. The method finds its most natural application in the study of rare events. Its capabilities are illustrated by nontrivial examples. The algorithm lends itself to straightforward parallelization, and when combined with ab initio molecular dynamics it promises to offer a powerful tool for the study of chemical reactions.

  19. Action-Derived Molecular Dynamics in the Study of Rare Events

    International Nuclear Information System (INIS)

    Passerone, Daniele; Parrinello, Michele

    2001-01-01

    We present a practical method to generate classical trajectories with fixed initial and final boundary conditions. Our method is based on the minimization of a suitably defined discretized action. The method finds its most natural application in the study of rare events. Its capabilities are illustrated by nontrivial examples. The algorithm lends itself to straightforward parallelization, and when combined with ab initio molecular dynamics it promises to offer a powerful tool for the study of chemical reactions

  20. Nanomaterials under extreme environments: A study of structural and dynamic properties using reactive molecular dynamics simulations

    Science.gov (United States)

    Shekhar, Adarsh

    Nanotechnology is becoming increasingly important with the continuing advances in experimental techniques. As researchers around the world are trying to expand the current understanding of the behavior of materials at the atomistic scale, the limited resolution of equipment, both in terms of time and space, act as roadblocks to a comprehensive study. Numerical methods, in general and molecular dynamics, in particular act as able compliment to the experiments in our quest for understanding material behavior. In this research work, large scale molecular dynamics simulations to gain insight into the mechano-chemical behavior under extreme conditions of a variety of systems with many real world applications. The body of this work is divided into three parts, each covering a particular system: 1) Aggregates of aluminum nanoparticles are good solid fuel due to high flame propagation rates. Multi-million atom molecular dynamics simulations reveal the mechanism underlying higher reaction rate in a chain of aluminum nanoparticles as compared to an isolated nanoparticle. This is due to the penetration of hot atoms from reacting nanoparticles to an adjacent, unreacted nanoparticle, which brings in external heat and initiates exothermic oxidation reactions. 2) Cavitation bubbles readily occur in fluids subjected to rapid changes in pressure. We use billion-atom reactive molecular dynamics simulations on a 163,840-processor BlueGene/P supercomputer to investigate chemical and mechanical damages caused by shock-induced collapse of nanobubbles in water near amorphous silica. Collapse of an empty nanobubble generates high-speed nanojet, resulting in the formation of a pit on the surface. The pit contains a large number of silanol groups and its volume is found to be directly proportional to the volume of the nanobubble. The gas-filled bubbles undergo partial collapse and consequently the damage on the silica surface is mitigated. 3) The structure and dynamics of water confined in

  1. Dynamics of the stochastic low concentration trimolecular oscillatory chemical system with jumps

    Science.gov (United States)

    Wei, Yongchang; Yang, Qigui

    2018-06-01

    This paper is devoted to discern long time dynamics through the stochastic low concentration trimolecular oscillatory chemical system with jumps. By Lyapunov technique, this system is proved to have a unique global positive solution, and the asymptotic stability in mean square of such model is further established. Moreover, the existence of random attractor and Lyapunov exponents are obtained for the stochastic homeomorphism flow generated by the corresponding global positive solution. And some numerical simulations are given to illustrate the presented results.

  2. Chemical Oscillations

    Indian Academy of Sciences (India)

    IMTECH),. Chandigarh. Praveen Kumar is pursuing his PhD in chemical dynamics at. Panjab University,. Chandigarh. Keywords. Chemical oscillations, autoca-. talYSis, Lotka-Volterra model, bistability, hysteresis, Briggs-. Rauscher reaction.

  3. An automated method to find transition states using chemical dynamics simulations.

    Science.gov (United States)

    Martínez-Núñez, Emilio

    2015-02-05

    A procedure to automatically find the transition states (TSs) of a molecular system (MS) is proposed. It has two components: high-energy chemical dynamics simulations (CDS), and an algorithm that analyzes the geometries along the trajectories to find reactive pathways. Two levels of electronic structure calculations are involved: a low level (LL) is used to integrate the trajectories and also to optimize the TSs, and a higher level (HL) is used to reoptimize the structures. The method has been tested in three MSs: formaldehyde, formic acid (FA), and vinyl cyanide (VC), using MOPAC2012 and Gaussian09 to run the LL and HL calculations, respectively. Both the efficacy and efficiency of the method are very good, with around 15 TS structures optimized every 10 trajectories, which gives a total of 7, 12, and 83 TSs for formaldehyde, FA, and VC, respectively. The use of CDS makes it a powerful tool to unveil possible nonstatistical behavior of the system under study. © 2014 Wiley Periodicals, Inc.

  4. 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.)

  5. 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)

    1999-12-31

    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.)

  6. 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.

  7. Chemical Arsenal for the Study of O-GlcNAc

    Directory of Open Access Journals (Sweden)

    Eun J. Kim

    2011-02-01

    Full Text Available The concepts of both protein glycosylation and cellular signaling have been influenced by O-linked-β-N-acetylglucosamine (O-GlcNAc modification (O-GlcNAcylation on the hydroxyl group of serine or threonine residues. Unlike conventional protein glycosylation, O-GlcNAcylation is localized in the nucleocytoplasm and its cycling is a dynamic process that operates in a highly regulated manner in response to various cellular stimuli. These characteristics render O-GlcNAcylation similar to phosphorylation, which has long been considered a major regulatory mechanism in cellular processes. Various efficient chemical approaches and novel mass spectrometric (MS techniques have uncovered numerous O-GlcNAcylated proteins that are involved in the regulation of many important cellular events. These discoveries imply that O-GlcNAcylation is another major regulator of cellular signaling. However, in contrast to phosphorylation, which is regulated by hundreds of kinases and phosphatases, dynamic O-GlcNAc cycling is catalyzed by only two enzymes: uridine diphospho-N-acetyl-glucosamine:polypeptide β-N-acetylglucosaminyl transferase (OGT and β-D-N-acetylglucosaminidase (OGA. Many useful chemical tools have recently been used to greatly expand our understanding of the extensive crosstalk between O-GlcNAcylation and phosphorylation and hence of cellular signaling. This review article describes the various useful chemical tools that have been developed and discusses the considerable advances made in the O-GlcNAc field.

  8. Dynamic Information Encoding With Dynamic Synapses in Neural Adaptation

    Science.gov (United States)

    Li, Luozheng; Mi, Yuanyuan; Zhang, Wenhao; Wang, Da-Hui; Wu, Si

    2018-01-01

    Adaptation refers to the general phenomenon that the neural system dynamically adjusts its response property according to the statistics of external inputs. In response to an invariant stimulation, neuronal firing rates first increase dramatically and then decrease gradually to a low level close to the background activity. This prompts a question: during the adaptation, how does the neural system encode the repeated stimulation with attenuated firing rates? It has been suggested that the neural system may employ a dynamical encoding strategy during the adaptation, the information of stimulus is mainly encoded by the strong independent spiking of neurons at the early stage of the adaptation; while the weak but synchronized activity of neurons encodes the stimulus information at the later stage of the adaptation. The previous study demonstrated that short-term facilitation (STF) of electrical synapses, which increases the synchronization between neurons, can provide a mechanism to realize dynamical encoding. In the present study, we further explore whether short-term plasticity (STP) of chemical synapses, an interaction form more common than electrical synapse in the cortex, can support dynamical encoding. We build a large-size network with chemical synapses between neurons. Notably, facilitation of chemical synapses only enhances pair-wise correlations between neurons mildly, but its effect on increasing synchronization of the network can be significant, and hence it can serve as a mechanism to convey the stimulus information. To read-out the stimulus information, we consider that a downstream neuron receives balanced excitatory and inhibitory inputs from the network, so that the downstream neuron only responds to synchronized firings of the network. Therefore, the response of the downstream neuron indicates the presence of the repeated stimulation. Overall, our study demonstrates that STP of chemical synapse can serve as a mechanism to realize dynamical neural

  9. 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

  10. Can disorder act as a chemical pressure? An optical study of the Hubbard model

    Science.gov (United States)

    Barman, H.; Laad, M. S.; Hassan, S. R.

    2018-05-01

    The optical properties have been studied using the dynamical mean-field theory on a disordered Hubbard model. Despite the fact that disorder turns a metal to an insulator in high dimensional correlated materials, we notice that it can enhance certain metallic behavior as if a chemical pressure is applied to the system resulting in an increase of the effective lattice bandwidth (BW). We study optical properties in such a scenario and compare results with experiments where the BW is changed through isovalent chemical substitution (keeping electron filling unaltered) and obtain remarkable similarities vindicating our claim. We also make the point that these similarities differ from some other forms of BW tuned optical effects.

  11. Chemical reactivity and spectroscopy explored from QM/MM molecular dynamics simulations using the LIO code

    Science.gov (United States)

    Marcolongo, Juan P.; Zeida, Ari; Semelak, Jonathan A.; Foglia, Nicolás O.; Morzan, Uriel N.; Estrin, Dario A.; González Lebrero, Mariano C.; Scherlis, Damián A.

    2018-03-01

    In this work we present the current advances in the development and the applications of LIO, a lab-made code designed for density functional theory calculations in graphical processing units (GPU), that can be coupled with different classical molecular dynamics engines. This code has been thoroughly optimized to perform efficient molecular dynamics simulations at the QM/MM DFT level, allowing for an exhaustive sampling of the configurational space. Selected examples are presented for the description of chemical reactivity in terms of free energy profiles, and also for the computation of optical properties, such as vibrational and electronic spectra in solvent and protein environments.

  12. Effects of chemical modifications on photophysics and exciton dynamics on {pi}-conjugation attenuated and metal-chelated photoconducting polymers

    Energy Technology Data Exchange (ETDEWEB)

    Chen, L. X.; Jager, W. J. H.; Gosztola, D. J.; Niemczyk, M. P.; Wasielewski, M. R.

    2000-03-11

    Effects of two types of chemical modifications on photoconducting polymers consisting of polyphenylenevinylene (PPV) derivatives are studied by static and ultrafast transient optical spectroscopy as well as semi-empirical ZINDO calculations. The first type of modification inserts 2,2{prime}-bipyridyl-5-vinylene units (bpy V) in the PPV backbone, and the second type involves metal-chelation with the bpy sites. Photoluminescence and exciton dynamics of polymers 1 and 2 with PV:bpyV ratios of 1 and 3 were examined in solution, and compared to those of the homopolymer, poly(2,5-bis(2{prime}-ethylhexyloxy)-1,4-phenylenevinylene) (BEH-PPV). Similar studies were carried out for several metal-chelated polymers. These results can be explained by changes in {pi}-conjugation throughout the polymer backbone. The attenuation in {pi}-conjugation by the chemical modifications transforms a conducting polymer from one-dimensional semiconductor to molecular aggregates.

  13. The RAVE-on Catalog of Stellar Atmospheric Parameters and Chemical Abundances for Chemo-dynamic Studies in the Gaia Era

    Energy Technology Data Exchange (ETDEWEB)

    Casey, Andrew R.; Hawkins, Keith; Koposov, Sergey; Sanders, Jason; Gilmore, Gerry [Institute of Astronomy, University of Cambridge, Madingley Road, Cambridge CB3 0HA (United Kingdom); Hogg, David W. [Simons Center for Data Analysis, 160 Fifth Avenue, 7th Floor, New York, NY 10010 (United States); Ness, Melissa; Rix, Hans-Walter [Max-Planck-Institut für Astronomie, Königstuhl 17, D-69117 Heidelberg (Germany); Kordopatis, Georges; Kunder, Andrea; Steinmetz, Matthias; Enke, Harry [Leibniz-Institut für Astrophysik Potsdam (AIP), An der Sternwarte 16, D-14482 Potsdam (Germany); Zwitter, Tomaž; Matijevič, Gal [University of Ljubljana, Faculty of Mathematics and Physics, Jadranska 19, 1000 Ljubljana (Slovenia); Freeman, Kenneth C.; Casagrande, Luca [Research School of Astronomy and Astrophysics, Mount Stromlo Observatory, The Australian National University, ACT 2611 (Australia); Seabroke, George [Mullard Space Science Laboratory, University College London, Holmbury St. Mary, Dorking, RH5 6NT (United Kingdom); Bienaymé, Olivier [Observatoire astronomique de Strasbourg, Université de Strasbourg, CNRS, UMR 7550, 11 rue de l’Université, F-67000 Strasbourg (France); Bland-Hawthorn, Joss [Sydney Institute for Astronomy, School of Physics, University of Sydney, NSW 2006 (Australia); Gibson, Brad K. [E.A. Milne Centre for Astrophysics, University of Hull, Hull, HU6 7RX (United Kingdom); and others

    2017-05-01

    The orbits, atmospheric parameters, chemical abundances, and ages of individual stars in the Milky Way provide the most comprehensive illustration of galaxy formation available. The Tycho- Gaia Astrometric Solution (TGAS) will deliver astrometric parameters for the largest ever sample of Milky Way stars, though its full potential cannot be realized without the addition of complementary spectroscopy. Among existing spectroscopic surveys, the RAdial Velocity Experiment (RAVE) has the largest overlap with TGAS (≳200,000 stars). We present a data-driven re-analysis of 520,781 RAVE spectra using The Cannon . For red giants, we build our model using high-fidelity APOGEE stellar parameters and abundances for stars that overlap with RAVE. For main sequence and sub-giant stars, our model uses stellar parameters from the K2/EPIC . We derive and validate effective temperature T {sub eff}, surface gravity log g , and chemical abundances of up to seven elements (O, Mg, Al, Si, Ca, Fe, and Ni). We report a total of 1,685,851 elemental abundances with a typical precision of 0.07 dex, a substantial improvement over previous RAVE data releases. The synthesis of RAVE-on and TGAS is the most powerful data set for chemo-dynamic analyses of the Milky Way ever produced.

  14. One- and two-dimensional chemical exchange nuclear magnetic resonance studies of the creatine kinase catalyzed reaction

    International Nuclear Information System (INIS)

    Gober, J.R.

    1988-01-01

    The equilibrium chemical exchange dynamics of the creatine kinase enzyme system were studied by one- and two-dimensional 31 P NMR techniques. Pseudo-first-order reaction rate constants were measured by the saturation transfer method under an array of experimental conditions of pH and temperature. Quantitative one-dimensional spectra were collected under the same conditions in order to calculate the forward and reverse reaction rates, the K eq , the hydrogen ion stoichiometry, and the standard thermodynamic functions. The pure absorption mode in four quadrant two-dimensional chemical exchange experiment was employed so that the complete kinetic matrix showing all of the chemical exchange process could be realized

  15. Combining NMR ensembles and molecular dynamics simulations provides more realistic models of protein structures in solution and leads to better chemical shift prediction

    International Nuclear Information System (INIS)

    Lehtivarjo, Juuso; Tuppurainen, Kari; Hassinen, Tommi; Laatikainen, Reino; Peräkylä, Mikael

    2012-01-01

    While chemical shifts are invaluable for obtaining structural information from proteins, they also offer one of the rare ways to obtain information about protein dynamics. A necessary tool in transforming chemical shifts into structural and dynamic information is chemical shift prediction. In our previous work we developed a method for 4D prediction of protein 1 H chemical shifts in which molecular motions, the 4th dimension, were modeled using molecular dynamics (MD) simulations. Although the approach clearly improved the prediction, the X-ray structures and single NMR conformers used in the model cannot be considered fully realistic models of protein in solution. In this work, NMR ensembles (NMRE) were used to expand the conformational space of proteins (e.g. side chains, flexible loops, termini), followed by MD simulations for each conformer to map the local fluctuations. Compared with the non-dynamic model, the NMRE+MD model gave 6–17% lower root-mean-square (RMS) errors for different backbone nuclei. The improved prediction indicates that NMR ensembles with MD simulations can be used to obtain a more realistic picture of protein structures in solutions and moreover underlines the importance of short and long time-scale dynamics for the prediction. The RMS errors of the NMRE+MD model were 0.24, 0.43, 0.98, 1.03, 1.16 and 2.39 ppm for 1 Hα, 1 HN, 13 Cα, 13 Cβ, 13 CO and backbone 15 N chemical shifts, respectively. The model is implemented in the prediction program 4DSPOT, available at http://www.uef.fi/4dspothttp://www.uef.fi/4dspot.

  16. Combining NMR ensembles and molecular dynamics simulations provides more realistic models of protein structures in solution and leads to better chemical shift prediction

    Energy Technology Data Exchange (ETDEWEB)

    Lehtivarjo, Juuso, E-mail: juuso.lehtivarjo@uef.fi; Tuppurainen, Kari; Hassinen, Tommi; Laatikainen, Reino [University of Eastern Finland, School of Pharmacy (Finland); Peraekylae, Mikael [University of Eastern Finland, Institute of Biomedicine (Finland)

    2012-03-15

    While chemical shifts are invaluable for obtaining structural information from proteins, they also offer one of the rare ways to obtain information about protein dynamics. A necessary tool in transforming chemical shifts into structural and dynamic information is chemical shift prediction. In our previous work we developed a method for 4D prediction of protein {sup 1}H chemical shifts in which molecular motions, the 4th dimension, were modeled using molecular dynamics (MD) simulations. Although the approach clearly improved the prediction, the X-ray structures and single NMR conformers used in the model cannot be considered fully realistic models of protein in solution. In this work, NMR ensembles (NMRE) were used to expand the conformational space of proteins (e.g. side chains, flexible loops, termini), followed by MD simulations for each conformer to map the local fluctuations. Compared with the non-dynamic model, the NMRE+MD model gave 6-17% lower root-mean-square (RMS) errors for different backbone nuclei. The improved prediction indicates that NMR ensembles with MD simulations can be used to obtain a more realistic picture of protein structures in solutions and moreover underlines the importance of short and long time-scale dynamics for the prediction. The RMS errors of the NMRE+MD model were 0.24, 0.43, 0.98, 1.03, 1.16 and 2.39 ppm for {sup 1}H{alpha}, {sup 1}HN, {sup 13}C{alpha}, {sup 13}C{beta}, {sup 13}CO and backbone {sup 15}N chemical shifts, respectively. The model is implemented in the prediction program 4DSPOT, available at http://www.uef.fi/4dspothttp://www.uef.fi/4dspot.

  17. Dynamic absorption coefficients of chemically amplified resists and nonchemically amplified resists at extreme ultraviolet

    Science.gov (United States)

    Fallica, Roberto; Stowers, Jason K.; Grenville, Andrew; Frommhold, Andreas; Robinson, Alex P. G.; Ekinci, Yasin

    2016-07-01

    The dynamic absorption coefficients of several chemically amplified resists (CAR) and non-CAR extreme ultraviolet (EUV) photoresists are measured experimentally using a specifically developed setup in transmission mode at the x-ray interference lithography beamline of the Swiss Light Source. The absorption coefficient α and the Dill parameters ABC were measured with unprecedented accuracy. In general, the α of resists match very closely with the theoretical value calculated from elemental densities and absorption coefficients, whereas exceptions are observed. In addition, through the direct measurements of the absorption coefficients and dose-to-clear values, we introduce a new figure of merit called chemical sensitivity to account for all the postabsorption chemical reaction ongoing in the resist, which also predicts a quantitative clearing volume and clearing radius, due to the photon absorption in the resist. These parameters may help provide deeper insight into the underlying mechanisms of the EUV concepts of clearing volume and clearing radius, which are then defined and quantitatively calculated.

  18. Contact Angle and Adhesion Dynamics and Hysteresis on Molecularly Smooth Chemically Homogeneous Surfaces.

    Science.gov (United States)

    Chen, Szu-Ying; Kaufman, Yair; Schrader, Alex M; Seo, Dongjin; Lee, Dong Woog; Page, Steven H; Koenig, Peter H; Isaacs, Sandra; Gizaw, Yonas; Israelachvili, Jacob N

    2017-09-26

    Measuring truly equilibrium adhesion energies or contact angles to obtain the thermodynamic values is experimentally difficult because it requires loading/unloading or advancing/receding boundaries to be measured at rates that can be slower than 1 nm/s. We have measured advancing-receding contact angles and loading-unloading adhesion energies for various systems and geometries involving molecularly smooth and chemically homogeneous surfaces moving at different but steady velocities in both directions, ±V, focusing on the thermodynamic limit of ±V → 0. We have used the Bell Theory (1978) to derive expressions for the dynamic (velocity-dependent) adhesion energies and contact angles suitable for both (i) dynamic adhesion measurements using the classic Johnson-Kendall-Roberts (JKR, 1971) theory of "contact mechanics" and (ii) dynamic contact angle hysteresis measurements of both rolling droplets and syringe-controlled (sessile) droplets on various surfaces. We present our results for systems that exhibited both steady and varying velocities from V ≈ 10 mm/s to 1 nm/s, where in all cases but one, the advancing (V > 0) and receding (V contact angles converged toward the same theoretical (thermodynamic) values as V → 0. Our equations for the dynamic contact angles are similar to the classic equations of Blake & Haynes (1969) and fitted the experimental adhesion data equally well over the range of velocities studied, although with somewhat different fitting parameters for the characteristic molecular length/dimension or area and characteristic bond formation/rupture lifetime or velocity. Our theoretical and experimental methods and results unify previous kinetic theories of adhesion and contact angle hysteresis and offer new experimental methods for testing kinetic models in the thermodynamic, quasi-static, limit. Our analyses are limited to kinetic effects only, and we conclude that hydrodynamic, i.e., viscous, and inertial effects do not play a role at the

  19. 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

  20. Chemical freeze-out study in proton-proton collisions at RHIC and LHC energies

    International Nuclear Information System (INIS)

    Das, Sabita; Mishra, Debadeepti; Mohanty, Bedangadas; Chatterjee, Sandeep

    2016-01-01

    Particle multiplicities measured at Relativistic Heavy Ion Collider (RHIC) and Large Hadron Collider (LHC) facilities can be used to understand the chemical freeze-out dynamics. At chemical freeze-out (CFO), inelastic collisions cease and the freeze-out parameters can be determined using measured particle multiplicities within the framework of a statistical model. The statistical model has proven to be quite successful in describing the particle production from elementary p-p and e"+e"- collisions up to heavy-ion collisions. It helps to do a systematic study of the centrality and energy dependence of freeze-out parameters in heavy-ion collisions from lower SPS to higher LHC energies. The new data at LHC along with the RHIC data can be used to do such a systematic study in proton-proton collisions

  1. Aldehyde-functionalized chitosan-montmorillonite films as dynamically-assembled, switchable-chemical release bioplastics.

    Science.gov (United States)

    Chabbi, Jamal; Jennah, Oumayma; Katir, Nadia; Lahcini, Mohamed; Bousmina, Mosto; El Kadib, Abdelkrim

    2018-03-01

    Temporal release of synergistic and/or complementary chemicals (e.g.: drugs) is recognized as extremely challenging because of their frequently intertwined kinetic delivery and presently, straightforward concepts enabling to circumvent this bottleneck are missing in the open literature. In this framework, we report herein on aldehyde-functionalized, transparent and flexible chitosan-montmorillonite hybrid films that act as a new generation of eco-friendly, controlled-chemical release bioplastics. These dynamically-assembled nanomaterials are designed by a ternary assembly from biowaste derived chitin biopolymer, aromatic aldehydes and layered clay nanoparticles. On the basis of their geometrical and conformational properties, the oxygenated groups on the grafted aromatics interact preferentially with either the base Schiff belonging to the carbohydrate (via intramolecular CNHO-Ar known as "imine clip") or with the hydroxyl groups belonging to the clay surface (via intermolecular Si-OHO-Ar). The exfoliated clay nanoparticles within the carbohydrate polymer enables either accelerating or slowing down of the imine (CN) hydrolysis depending on the interaction of the conjugated aromatics. This provides the driving force for fine tuning host-guest interactions at the molecular level and constitutes an entry toward subtle discrimination of different chemicals (e.g. complementary fertilizers, synergistic drugs) during their sequential release. Copyright © 2017 Elsevier Ltd. All rights reserved.

  2. Experimental studies of thermal and chemical interactions between molten aluminum and water

    Energy Technology Data Exchange (ETDEWEB)

    Farahani, A.A.; Corradini, M.L. [Univ. of Wisconsin, Madison, WI (United States)

    1995-09-01

    The possibility of rapid physical and chemical aluminum/water interactions during a core melt accident in a noncommercial reactor (e.g., HFIR, ATR) has resulted in extensive research to determine the mechanism by which these interactions occur and propagate on an explosive time scale. These events have been reported in nuclear testing facilities, i.e., during SPERT 1D experiment, and also in aluminum casting industries. Although rapid chemical reactions between molten aluminum and water have been subject of many studies, very few reliable measurements of the extent of the chemical reactions have thus far been made. We have modified an existing 1-D shock tube facility to perform experiments in order to determine the extent of the explosive thermal/chemical interactions between molton aluminum and water by measuring important physical quantities such as the maximum dynamic pressure and the amount of the generated hydrogen. Experimental results show that transient pressures greater than 69 MPa with a rise time of less than 125 {mu}sec can occur as the result of the chemical reaction of 4.2 grams of molton aluminum (approximately 15% of the total mass of the fuel of 28 grams) at 980 C with room temperature water.

  3. 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.

  4. Chemical Reactivity and Spectroscopy Explored From QM/MM Molecular Dynamics Simulations Using the LIO Code

    Directory of Open Access Journals (Sweden)

    Juan P. Marcolongo

    2018-03-01

    Full Text Available In this work we present the current advances in the development and the applications of LIO, a lab-made code designed for density functional theory calculations in graphical processing units (GPU, that can be coupled with different classical molecular dynamics engines. This code has been thoroughly optimized to perform efficient molecular dynamics simulations at the QM/MM DFT level, allowing for an exhaustive sampling of the configurational space. Selected examples are presented for the description of chemical reactivity in terms of free energy profiles, and also for the computation of optical properties, such as vibrational and electronic spectra in solvent and protein environments.

  5. Dynamics of chemical elements in the fermentation process of ethanol production

    International Nuclear Information System (INIS)

    Nepomuceno, N.; Fernandes, E.A.N.; Bacchi, M.A.

    1997-01-01

    Brazil has become the largest producer of biomass ethanol derived from sugar cane. The industrial production is based on the fermentation of sugar cane juice by yeast, inside of large volume vats, in a fed-batch process that recycles yeast cells. To study the dynamics of chemical elements in each operating cycle, five stages of the fermentation process were considered: must, yeast suspension, wine, non-yeast wine and yeast cream. For this, a mass balance of the terrigenous elements, Ce, Co, Cs, Eu, Fe, Hf, La, Na, Sc, Sm, and Th, and the sugar cane plant elements, Br, K, Rb, and Zn, were established in fermentation vats of an industrial scale unit, with sampling undertaken during different climatic conditions (dry and rainy periods). A similar distribution of the sugar cane characteristics elements was found for the stages analysed, while for the terrigenous elements a trend of accumulation in the yeast cream was observed. Preferential absorption of Br, K, Rb, and Zn by yeast cells was indicated by the smaller concentrations observed in yeast suspension than in yeast cream. (author)

  6. 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.

    2016-01-01

    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 63-90N 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 13 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.

  7. Chemical Sciences Division annual report 1994

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1995-06-01

    The division is one of ten LBL research divisions. It is composed of individual research groups organized into 5 scientific areas: chemical physics, inorganic/organometallic chemistry, actinide chemistry, atomic physics, and chemical engineering. Studies include structure and reactivity of critical reaction intermediates, transients and dynamics of elementary chemical reactions, and heterogeneous and homogeneous catalysis. Work for others included studies of superconducting properties of high-{Tc} oxides. In FY 1994, the division neared completion of two end-stations and a beamline for the Advanced Light Source, which will be used for combustion and other studies. This document presents summaries of the studies.

  8. Vibrational studies of Thyroxine hormone: Comparative study with quantum chemical calculations

    Science.gov (United States)

    Borah, Mukunda Madhab; Devi, Th. Gomti

    2017-11-01

    The FTIR and Raman techniques have been used to record spectra of Thyroxine. The stable geometrical parameters and vibrational wave numbers were calculated based on potential energy distribution (PED) using vibrational energy distribution analysis (VEDA) program. The vibrational energies are assigned to monomer, chain dimer and cyclic dimers of this molecule using the basis set B3LYP/LANL2DZ. The computational scaled frequencies are in good agreements with the experimental results. The study is extended to calculate the HOMO-LUMO energy gap, Molecular Electrostatic Potential (MEP) surface, hardness (η), chemical potential (μ), Global electrophilicity index (ω) and different thermo dynamical properties of Thyroxine in different states. The calculated HOMO-LUMO energies show the charge transfer occurs within the molecule. The calculated Natural bond orbital (NBO) analysis confirms the presence of intra-molecular charge transfer as well as the hydrogen bonding interaction.

  9. Frontiers in Chemical Physics

    Energy Technology Data Exchange (ETDEWEB)

    Bowlan, Pamela Renee [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

    2016-05-02

    These are slides dealing with frontiers in chemical physics. The following topics are covered: Time resolving chemistry with ultrashort pulses in the 0.1-40 THz spectral range; Example: Mid-infrared absorption spectrum of the intermediate state CH2OO; Tracking reaction dynamics through changes in the spectra; Single-shot measurement of the mid-IR absorption dynamics; Applying 2D coherent mid-IR spectroscopy to learn more about transition states; Time resolving chemical reactions at a catalysis using mid-IR and THz pulses; Studying topological insulators requires a surface sensitive probe; Nonlinear phonon dynamics in Bi2Se3; THz-pump, SHG-probe as a surface sensitive coherent 2D spectroscopy; Nanometer and femtosecond spatiotemporal resolution mid-IR spectroscopy; Coherent two-dimensional THz/mid-IR spectroscopy with 10nm spatial resolution; Pervoskite oxides as catalysts; Functionalized graphene for catalysis; Single-shot spatiotemporal measurements; Spatiotemporal pulse measurement; Intense, broad-band THz/mid-IR generation with organic crystals.

  10. Method for the deconvolution of incompletely resolved CARS spectra in chemical dynamics experiments

    International Nuclear Information System (INIS)

    Anda, A.A.; Phillips, D.L.; Valentini, J.J.

    1986-01-01

    We describe a method for deconvoluting incompletely resolved CARS spectra to obtain quantum state population distributions. No particular form for the rotational and vibrational state distribution is assumed, the population of each quantum state is treated as an independent quantity. This method of analysis differs from previously developed approaches for the deconvolution of CARS spectra, all of which assume that the population distribution is Boltzmann, and thus are limited to the analysis of CARS spectra taken under conditions of thermal equilibrium. The method of analysis reported here has been developed to deconvolute CARS spectra of photofragments and chemical reaction products obtained in chemical dynamics experiments under nonequilibrium conditions. The deconvolution procedure has been incorporated into a computer code. The application of that code to the deconvolution of CARS spectra obtained for samples at thermal equilibrium and not at thermal equilibrium is reported. The method is accurate and computationally efficient

  11. High-speed AFM for Studying Dynamic Biomolecular Processes

    Science.gov (United States)

    Ando, Toshio

    2008-03-01

    Biological molecules show their vital activities only in aqueous solutions. It had been one of dreams in biological sciences to directly observe biological macromolecules (protein, DNA) at work under a physiological condition because such observation is straightforward to understanding their dynamic behaviors and functional mechanisms. Optical microscopy has no sufficient spatial resolution and electron microscopy is not applicable to in-liquid samples. Atomic force microscopy (AFM) can visualize molecules in liquids at high resolution but its imaging rate was too low to capture dynamic biological processes. This slow imaging rate is because AFM employs mechanical probes (cantilevers) and mechanical scanners to detect the sample height at each pixel. It is quite difficult to quickly move a mechanical device of macroscopic size with sub-nanometer accuracy without producing unwanted vibrations. It is also difficult to maintain the delicate contact between a probe tip and fragile samples. Two key techniques are required to realize high-speed AFM for biological research; fast feedback control to maintain a weak tip-sample interaction force and a technique to suppress mechanical vibrations of the scanner. Various efforts have been carried out in the past decade to materialize high-speed AFM. The current high-speed AFM can capture images on video at 30-60 frames/s for a scan range of 250nm and 100 scan lines, without significantly disturbing week biomolecular interaction. Our recent studies demonstrated that this new microscope can reveal biomolecular processes such as myosin V walking along actin tracks and association/dissociation dynamics of chaperonin GroEL-GroES that occurs in a negatively cooperative manner. The capacity of nanometer-scale visualization of dynamic processes in liquids will innovate on biological research. In addition, it will open a new way to study dynamic chemical/physical processes of various phenomena that occur at the liquid-solid interfaces.

  12. Using Analogies to Prevent Misconceptions about Chemical Equilibrium

    Science.gov (United States)

    Sahin Pekmez, Esin

    2010-01-01

    The main purpose of this study was to find the effectiveness of using analogies to prevent misconceptions about chemical equilibrium. Nineteen analogies, which were based on dynamic aspects of chemical equilibrium and application of Le Chatelier's principle, were developed. The participations of this study consisted of 11th grade students (n: 151)…

  13. The dynamic behavior of chemically "stiffened" red blood cells in microchannel flows.

    Science.gov (United States)

    Forsyth, Alison M; Wan, Jiandi; Ristenpart, William D; Stone, Howard A

    2010-07-01

    The rigidity of red blood cells (RBCs) plays an important role in whole blood viscosity and is correlated with several cardiovascular diseases. Two chemical agents that are commonly used to study cell deformation are diamide and glutaraldehyde. Despite diamide's common usage, there are discrepancies in the literature surrounding diamide's effect on the deformation of RBCs in shear and pressure-driven flows; in particular, shear flow experiments have shown that diamide stiffens cells, while pressure-driven flow in capillaries did not give this result. We performed pressure-driven flow experiments with RBCs in a microfluidic constriction and quantified the cell dynamics using high-speed imaging. Diamide, which affects RBCs by cross-linking spectrin skeletal membrane proteins, did not reduce deformation and showed an unchanged effective strain rate when compared to healthy cells. In contrast, glutaraldehyde, which is a non-specific fixative that acts on all components of the cell, did reduce deformation and showed increased instances of tumbling, both of which are characteristic features of stiffened, or rigidified, cells. Because glutaraldehyde increases the effective viscosity of the cytoplasm and lipid membrane while diamide does not, one possible explanation for our results is that viscous effects in the cytoplasm and/or lipid membrane are a dominant factor in dictating dynamic responses of RBCs in pressure-driven flows. Finally, literature on the use of diamide as a stiffening agent is summarized, and provides supporting evidence for our conclusions. Copyright 2010 Elsevier Inc. All rights reserved.

  14. Chemical equilibration of antihyperons

    International Nuclear Information System (INIS)

    Greiner, C.

    2002-01-01

    Rapid chemical equilibration of antihyperons by means of the interplay between strong annihilation on baryons and the corresponding backreactions of multi-mesonic (fusion-type) processes in the later, hadronic stage of an ultrarelativistic heavy ion collision will be discussed. Explicit rate calculations for a dynamical setup are presented. At maximum SPS energies yields of each antihyperon specie are obtained which are consistent with chemical saturated populations of T∼150-160 MeV. The proposed picture supports dynamically the popular chemical freeze-out parameters extracted within thermal models. (orig.)

  15. 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

  16. Elastic properties of amorphous boron suboxide based solids studied using ab initio molecular dynamics

    International Nuclear Information System (INIS)

    Music, Denis; Schneider, Jochen M

    2008-01-01

    We have studied the correlation between chemical composition, structure, chemical bonding and elastic properties of amorphous B 6 O based solids using ab initio molecular dynamics. These solids are of different chemical compositions, but the elasticity data appear to be a function of density. This is in agreement with previous experimental observations. As the density increases from 1.64 to 2.38 g cm -3 , the elastic modulus increases from 74 to 253 GPa. This may be understood by analyzing the cohesive energy and the chemical bonding of these compounds. The cohesive energy decreases from -7.051 to -7.584 eV/atom in the elastic modulus range studied. On the basis of the electron density distributions, Mulliken analysis and radial distribution functions, icosahedral bonding is the dominating bonding type. C and N promote cross-linking of icosahedra and thus increase the density, while H hinders the cross-linking by forming OH groups. The presence of icosahedral bonding is independent of the density

  17. Modeling chemical kinetics graphically

    NARCIS (Netherlands)

    Heck, A.

    2012-01-01

    In literature on chemistry education it has often been suggested that students, at high school level and beyond, can benefit in their studies of chemical kinetics from computer supported activities. Use of system dynamics modeling software is one of the suggested quantitative approaches that could

  18. A New Theoretical Approach to Single-Molecule Fluorescence Optical Studies of RNA Dynamics

    International Nuclear Information System (INIS)

    Zhao Xinghai; Shan Guangcun; Bao Shuying

    2011-01-01

    Single-molecule fluorescence spectroscopy in condensed phases has many important chemical and biological applications. The single-molecule fluorescence measurements contain information about conformational dynamics on a vast range of time scales. Based on the data analysis protocols methodology proposed by X. Sunney Xie, the theoretical study here mainly focuses on the single-molecule studies of single RNA with interconversions among different conformational states, to with a single FRET pair attached. We obtain analytical expressions for fluorescence lifetime correlation functions that relate changes in fluorescence lifetime to the distance-dependent FRET mechanism within the context of the Smoluchowski diffusion model. The present work establishes useful guideline for the single-molecule studies of biomolecules to reveal the complicated folding dynamics of single RNA molecules at nanometer scale.

  19. Advanced Chemical Propulsion Study

    Science.gov (United States)

    Woodcock, Gordon; Byers, Dave; Alexander, Leslie A.; Krebsbach, Al

    2004-01-01

    A study was performed of advanced chemical propulsion technology application to space science (Code S) missions. The purpose was to begin the process of selecting chemical propulsion technology advancement activities that would provide greatest benefits to Code S missions. Several missions were selected from Code S planning data, and a range of advanced chemical propulsion options was analyzed to assess capabilities and benefits re these missions. Selected beneficial applications were found for higher-performing bipropellants, gelled propellants, and cryogenic propellants. Technology advancement recommendations included cryocoolers and small turbopump engines for cryogenic propellants; space storable propellants such as LOX-hydrazine; and advanced monopropellants. It was noted that fluorine-bearing oxidizers offer performance gains over more benign oxidizers. Potential benefits were observed for gelled propellants that could be allowed to freeze, then thawed for use.

  20. Chemical dynamics of the first proton-coupled electron transfer of water oxidation on TiO2 anatase.

    Science.gov (United States)

    Chen, Jia; Li, Ye-Fei; Sit, Patrick; Selloni, Annabella

    2013-12-18

    Titanium dioxide (TiO2) is a prototype, water-splitting (photo)catalyst, but its performance is limited by the large overpotential for the oxygen evolution reaction (OER). We report here a first-principles density functional theory study of the chemical dynamics of the first proton-coupled electron transfer (PCET), which is considered responsible for the large OER overpotential on TiO2. We use a periodic model of the TiO2/water interface that includes a slab of anatase TiO2 and explicit water molecules, sample the solvent configurations by first principles molecular dynamics, and determine the energy profiles of the two electronic states involved in the electron transfer (ET) by hybrid functional calculations. Our results suggest that the first PCET is sequential, with the ET following the proton transfer. The ET occurs via an inner sphere process, which is facilitated by a state in which one electronic hole is shared by the two oxygen ions involved in the transfer.

  1. Multi-fractal characterization of bacterial swimming dynamics: a case study on real and simulated Serratia marcescens

    OpenAIRE

    Koorehdavoudi, Hana; Bogdan, Paul; Wei, Guopeng; Marculescu, Radu; Zhuang, Jiang; Carlsen, Rika Wright; Sitti, Metin

    2017-01-01

    To add to the current state of knowledge about bacterial swimming dynamics, in this paper, we study the fractal swimming dynamics of populations of Serratia marcescens bacteria both in vitro and in silico, while accounting for realistic conditions like volume exclusion, chemical interactions, obstacles and distribution of chemoattractant in the environment. While previous research has shown that bacterial motion is non-ergodic, we demonstrate that, besides the non-ergodicity, the bacterial sw...

  2. Dynamics of shearing force and its correlations with chemical compositions and in vitro dry matter digestibility of stylo (Stylosanthes guianensis) stem.

    Science.gov (United States)

    Zi, Xuejuan; Li, Mao; Zhou, Hanlin; Tang, Jun; Cai, Yimin

    2017-12-01

    The study explored the dynamics of shearing force and its correlation with chemical compositions and in vitro dry matter digestibility (IVDMD) of stylo. The shearing force, diameter, linear density, chemical composition, and IVDMD of different height stylo stem were investigated. Linear regression analysis was done to determine the relationships between the shearing force and cut height, diameter, chemical composition, or IVDMD. The results showed that shearing force of stylo stem increased with plant height increasing and the crude protein (CP) content and IVDMD decreased but fiber content increased over time, resulting in decreased forage value. In addition, tall stem had greater shearing force than short stem. Moreover, shearing force is positively correlated with stem diameter, linear density and fiber fraction, but negatively correlated with CP content and IVDMD. Overall, shearing force is an indicator more direct, easier and faster to measure than chemical composition and digestibility for evaluation of forage nutritive value related to animal performance. Therefore, it can be used to evaluate the nutritive value of stylo.

  3. STUDY REGARDING THE CORELATION BETWEEN SOMATIC CELLS COUNT AND MAJOR CHEMICAL COMPOUNDS IN RAW MILK

    Directory of Open Access Journals (Sweden)

    S. ACATINCĂI

    2008-10-01

    Full Text Available This study approaches the dynamic of somatic cells number and chemical composition of milk during 13 months of control. The study also investigates the correlations between the number of somatic cells and some chemical parameters in milk. Studies were carried out on Romanian Black and White cows between March 2005 and March 2006 at the Didactical farm of the Banat University of Agricultural Sciences Timisoara. As quality indicator, the number of somatic cells has different values among the controls. Average values for the 13 months of control, with the exception of three controls, were below maximum limit admitted from 1th of January 2007 (600000 SCC/ml milk. There weren’t any significant differences for SCC between the two seasons. Chemical parameters in milk varied in close limits and the differences were not significant, with one exception for fat percent. Fat percent is higher (p<0.05 in the cold season 3.87% compared with 3.55% during the warm season. Somatic cells number is weak correlated with lactose and strong correlated with proteins.

  4. Semiclassical methods in chemical reaction dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Keshavamurthy, Srihari [Univ. of California, Berkeley, CA (United States)

    1994-12-01

    Semiclassical approximations, simple as well as rigorous, are formulated in order to be able to describe gas phase chemical reactions in large systems. We formulate a simple but accurate semiclassical model for incorporating multidimensional tunneling in classical trajectory simulations. This model is based on the existence of locally conserved actions around the saddle point region on a multidimensional potential energy surface. Using classical perturbation theory and monitoring the imaginary action as a function of time along a classical trajectory we calculate state-specific unimolecular decay rates for a model two dimensional potential with coupling. Results are in good comparison with exact quantum results for the potential over a wide range of coupling constants. We propose a new semiclassical hybrid method to calculate state-to-state S-matrix elements for bimolecular reactive scattering. The accuracy of the Van Vleck-Gutzwiller propagator and the short time dynamics of the system make this method self-consistent and accurate. We also go beyond the stationary phase approximation by doing the resulting integrals exactly (numerically). As a result, classically forbidden probabilties are calculated with purely real time classical trajectories within this approach. Application to the one dimensional Eckart barrier demonstrates the accuracy of this approach. Successful application of the semiclassical hybrid approach to collinear reactive scattering is prevented by the phenomenon of chaotic scattering. The modified Filinov approach to evaluating the integrals is discussed, but application to collinear systems requires a more careful analysis. In three and higher dimensional scattering systems, chaotic scattering is suppressed and hence the accuracy and usefulness of the semiclassical method should be tested for such systems.

  5. Semiclassical methods in chemical reaction dynamics

    International Nuclear Information System (INIS)

    Keshavamurthy, S.

    1994-12-01

    Semiclassical approximations, simple as well as rigorous, are formulated in order to be able to describe gas phase chemical reactions in large systems. We formulate a simple but accurate semiclassical model for incorporating multidimensional tunneling in classical trajectory simulations. This model is based on the existence of locally conserved actions around the saddle point region on a multidimensional potential energy surface. Using classical perturbation theory and monitoring the imaginary action as a function of time along a classical trajectory we calculate state-specific unimolecular decay rates for a model two dimensional potential with coupling. Results are in good comparison with exact quantum results for the potential over a wide range of coupling constants. We propose a new semiclassical hybrid method to calculate state-to-state S-matrix elements for bimolecular reactive scattering. The accuracy of the Van Vleck-Gutzwiller propagator and the short time dynamics of the system make this method self-consistent and accurate. We also go beyond the stationary phase approximation by doing the resulting integrals exactly (numerically). As a result, classically forbidden probabilties are calculated with purely real time classical trajectories within this approach. Application to the one dimensional Eckart barrier demonstrates the accuracy of this approach. Successful application of the semiclassical hybrid approach to collinear reactive scattering is prevented by the phenomenon of chaotic scattering. The modified Filinov approach to evaluating the integrals is discussed, but application to collinear systems requires a more careful analysis. In three and higher dimensional scattering systems, chaotic scattering is suppressed and hence the accuracy and usefulness of the semiclassical method should be tested for such systems

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

    Science.gov (United States)

    Sonne, Anne Th; McKnight, Ursula S; Rønde, Vinni; Bjerg, Poul L

    2017-11-15

    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, are challenging to assess with multiple chemical stressors impacting stream corridors. New approaches are urgently needed for identifying relevant sources, pathways and potential impacts for implementation of suitable source management and remedial measures. We developed a method for risk assessing chemical 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 of all three stream compartments - stream water, hyporheic zone, streambed sediment - made it possible to link chemical stressors to their respective sources and obtain new knowledge about source composition and origin. Moreover, toxic unit estimation and comparison to environmental standards revealed 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 of chlorinated ethenes and pharmaceutical compounds discharge into the stream every year. The strongly reduced redox conditions in the plume result in high concentrations of dissolved iron and additionally release arsenic, generating the complex contaminant mixture found in the narrow discharge zone. The fingerprint of the plume was observed in the stream several km downgradient, while nutrients, inorganics and pesticides played a minor role for the stream health. The

  7. Journal of Chemical Sciences | Indian Academy of Sciences

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences. K Anbalagan. Articles written in Journal of Chemical Sciences. Volume 116 Issue 2 March 2004 pp 119-127. Adsorption dynamics and equilibrium studies of Zn (II) onto chitosan · G Karthikeyan K Anbalagan N Muthulakshmi Andal · More Details Abstract Fulltext PDF.

  8. Journal of Chemical Sciences | Indian Academy of Sciences

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences. G Karthikeyan. Articles written in Journal of Chemical Sciences. Volume 116 Issue 2 March 2004 pp 119-127. Adsorption dynamics and equilibrium studies of Zn (II) onto chitosan · G Karthikeyan K Anbalagan N Muthulakshmi Andal · More Details Abstract Fulltext PDF.

  9. A Molecular Dynamics Study of the Structural and Dynamical Properties of Putative Arsenic Substituted Lipid Bilayers

    Directory of Open Access Journals (Sweden)

    Ratna Juwita

    2013-04-01

    Full Text Available Cell membranes are composed mainly of phospholipids which are in turn, composed of five major chemical elements: carbon, hydrogen, nitrogen, oxygen, and phosphorus. Recent studies have suggested the possibility of sustaining life if the phosphorus is substituted by arsenic. Although this issue is still controversial, it is of interest to investigate the properties of arsenated-lipid bilayers to evaluate this possibility. In this study, we simulated arsenated-lipid, 1-palmitoyl-2-oleoyl-sn-glycero-3-arsenocholine (POAC, lipid bilayers using all-atom molecular dynamics to understand basic structural and dynamical properties, in particular, the differences from analogous 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine, (POPC lipid bilayers. Our simulations showed that POAC lipid bilayers have distinct structural and dynamical properties from those of native POPC lipid bilayers. Relative to POPC lipid bilayers, POAC lipid bilayers have a more compact structure with smaller lateral areas and greater order. The compact structure of POAC lipid bilayers is due to the fact that more inter-lipid salt bridges are formed with arsenate-choline compared to the phosphate-choline of POPC lipid bilayers. These inter-lipid salt bridges bind POAC lipids together and also slow down the head group rotation and lateral diffusion of POAC lipids. Thus, it would be anticipated that POAC and POPC lipid bilayers would have different biological implications.

  10. Chemical industrial areas and their dynamic danger behaviour

    NARCIS (Netherlands)

    Reniers, Genserik L L; Audenaert, Amaryllis; Dullaert, W.; Soudan, K.

    2007-01-01

    Chemical industrial areas or so-called chemical clusters consist of various companies situated next to each other. Such areas are composed of hundreds of chemical installations exhibiting danger to a certain degree for initiating or continuing knock-on effects. In this paper, a methodology to model

  11. Molecular dynamics simulation of chemical vapor deposition of amorphous carbon. Dependence on H/C ratio of source gas

    International Nuclear Information System (INIS)

    Ito, Atsushi M.; Takayama, Arimichi; Nakamura, Hiroaki; Saito, Seiki; Ohno, Noriyasu; Kajita, Shin

    2011-01-01

    By molecular dynamics simulation, the chemical vapor deposition of amorphous carbon onto graphite and diamond surfaces was studied. In particular, we investigated the effect of source H/C ratio, which is the ratio of the number of hydrogen atoms to the number of carbon atoms in a source gas, on the deposition process. In the present simulation, the following two source gas conditions were tested: one was that the source gas was injected as isolated carbon and hydrogen atoms, and the other was that the source gas was injected as hydrocarbon molecules. Under the former condition, we found that as the source H/C ratio increases, the deposition rate of carbon atoms decreases exponentially. This exponential decrease in the deposition rate with increasing source H/C ratio agrees with experimental data. However, under the latter molecular source condition, the deposition rate did not decrease exponentially because of a chemical reaction peculiar to the type of hydrocarbon in the source gas. (author)

  12. 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. [Univ. of Chicago, IL (United States). James Franck Inst. and Dept. of Chemistry

    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

  13. Chemical process control using Mat lab

    International Nuclear Information System (INIS)

    Kang, Sin Chun; Kim, Raeh Yeon; Kim, Yang Su; Oh, Min; Yeo, Yeong Gu; Jung, Yeon Su

    2001-07-01

    This book is about chemical process control, which includes the basis of process control with conception, function, composition of system and summary, change of laplace and linearization, modeling of chemical process, transfer function and block diagram, the first dynamic property of process, the second dynamic property of process, the dynamic property of combined process, control structure of feedback on component of control system, the dynamic property of feedback control loop, stability of closed loop control structure, expression of process, modification and composition of controller, analysis of vibration response and adjustment controller using vibration response.

  14. Probabilistic validation of protein NMR chemical shift assignments

    International Nuclear Information System (INIS)

    Dashti, Hesam; Tonelli, Marco; Lee, Woonghee; Westler, William M.; Cornilescu, Gabriel; Ulrich, Eldon L.; Markley, John L.

    2016-01-01

    Data validation plays an important role in ensuring the reliability and reproducibility of studies. NMR investigations of the functional properties, dynamics, chemical kinetics, and structures of proteins depend critically on the correctness of chemical shift assignments. We present a novel probabilistic method named ARECA for validating chemical shift assignments that relies on the nuclear Overhauser effect data. ARECA has been evaluated through its application to 26 case studies and has been shown to be complementary to, and usually more reliable than, approaches based on chemical shift databases. ARECA is available online at http://areca.nmrfam.wisc.edu/ http://areca.nmrfam.wisc.edu/

  15. Probabilistic validation of protein NMR chemical shift assignments

    Energy Technology Data Exchange (ETDEWEB)

    Dashti, Hesam [University of Wisconsin-Madison, Graduate Program in Biophysics, Biochemistry Department (United States); Tonelli, Marco; Lee, Woonghee; Westler, William M.; Cornilescu, Gabriel [University of Wisconsin-Madison, Biochemistry Department, National Magnetic Resonance Facility at Madison (United States); Ulrich, Eldon L. [University of Wisconsin-Madison, BioMagResBank, Biochemistry Department (United States); Markley, John L., E-mail: markley@nmrfam.wisc.edu, E-mail: jmarkley@wisc.edu [University of Wisconsin-Madison, Biochemistry Department, National Magnetic Resonance Facility at Madison (United States)

    2016-01-15

    Data validation plays an important role in ensuring the reliability and reproducibility of studies. NMR investigations of the functional properties, dynamics, chemical kinetics, and structures of proteins depend critically on the correctness of chemical shift assignments. We present a novel probabilistic method named ARECA for validating chemical shift assignments that relies on the nuclear Overhauser effect data. ARECA has been evaluated through its application to 26 case studies and has been shown to be complementary to, and usually more reliable than, approaches based on chemical shift databases. ARECA is available online at http://areca.nmrfam.wisc.edu/ http://areca.nmrfam.wisc.edu/.

  16. Silver-mediated base pairings: towards dynamic DNA nanostructures with enhanced chemical and thermal stability

    International Nuclear Information System (INIS)

    Swasey, Steven M; Gwinn, Elisabeth G

    2016-01-01

    The thermal and chemical fragility of DNA nanomaterials assembled by Watson–Crick (WC) pairing constrain the settings in which these materials can be used and how they can be functionalized. Here we investigate use of the silver cation, Ag + , as an agent for more robust, metal-mediated self-assembly, focusing on the simplest duplex building blocks that would be required for more elaborate Ag + –DNA nanostructures. Our studies of Ag + -induced assembly of non-complementary DNA oligomers employ strands of 2–24 bases, with varied base compositions, and use electrospray ionization mass spectrometry to determine product compositions. High yields of duplex products containing narrowly distributed numbers of Ag + can be achieved by optimizing solution conditions. These Ag + -mediated duplexes are stable to at least 60 mM Mg 2+ , higher than is necessary for WC nanotechnology schemes such as tile assemblies and DNA origami, indicating that sequential stages of Ag + -mediated and WC-mediated assembly may be feasible. Circular dichroism spectroscopy suggests simple helical structures for Ag + -mediated duplexes with lengths to at least 20 base pairs, and further indicates that the structure of cytosine-rich duplexes is preserved at high urea concentrations. We therefore propose an approach towards dynamic DNA nanomaterials with enhanced thermal and chemical stability through designs that combine sturdy silver-mediated ‘frames’ with WC paired ‘pictures’. (paper)

  17. Chemical phenomena under severe accident conditions

    International Nuclear Information System (INIS)

    Powers, D.A.

    1988-01-01

    A severe nuclear reactor accident is expected to involve a vast number of chemical processes. The chemical processes of major safety significance begin with the production of hydrogen during steam oxidation of fuel cladding. Physico-chemical changes in the fuel and the vaporization of radionuclides during reactor accidents have captured much of the attention of the safety community in recent years. Protracted chemical interactions of core debris with structural concrete mark the conclusion of dynamic events in a severe accident. An overview of the current understanding of chemical processes in severe reactor accident is provided in this paper. It is shown that most of this understanding has come from application of findings from other fields though a few areas have in the past been subject to in-depth study of a fundamental nature. Challenges in the study of severe accident chemistry are delineated

  18. Pair Interaction of Catalytical Sphere Dimers in Chemically Active Media

    Directory of Open Access Journals (Sweden)

    Jing-Min Shi

    2018-01-01

    Full Text Available We study the pair dynamics of two self-propelled sphere dimers in the chemically active medium in which a cubic autocatalytic chemical reaction takes place. Concentration gradient around the dimer, created by reactions occurring on the catalytic sphere surface and responsible for the self-propulsion, is greatly influenced by the chemical activities of the environment. Consequently, the pair dynamics of two dimers mediated by the concentration field are affected. In the particle-based mesoscopic simulation, we combine molecular dynamics (MD for potential interactions and reactive multiparticle collision dynamics (RMPC for solvent flow and bulk reactions. Our results indicate three different configurations between a pair of dimers after the collision, i.e., two possible scenarios of bound dimer pairs and one unbound dimer pair. A phase diagram is sketched as a function of the rate coefficients of the environment reactions. Since the pair interactions are the basic elements of larger scale systems, we believe the results may shed light on the understanding of the collective dynamics.

  19. Combinatorial computational chemistry approach of tight-binding quantum chemical molecular dynamics method to the design of the automotive catalysts

    International Nuclear Information System (INIS)

    Ito, Yuki; Jung, Changho; Luo, Yi; Koyama, Michihisa; Endou, Akira; Kubo, Momoji; Imamura, Akira; Miyamoto, Akira

    2006-01-01

    Recently, we have developed a new tight-binding quantum chemical molecular dynamics program 'Colors' for combinatorial computational chemistry approach. This methodology is based on our original tight-binding approximation and realized over 5000 times acceleration compared to the conventional first-principles molecular dynamics method. In the present study, we applied our new program to the simulations on various realistic large-scale models of the automotive three-way catalysts, ultrafine Pt particle/CeO 2 (111) support. Significant electron transfer from the Pt particle to the CeO 2 (111) surface was observed and it was found to strongly depend on the size of the Pt particle. Furthermore, our simulation results suggest that the reduction of the Ce atom due to the electron transfer from the Pt particle to the CeO 2 surface is a main reason for the strong interaction of the Pt particle and CeO 2 (111) support

  20. EXAFS characterization of supported metal catalysts in chemically dynamic environments

    International Nuclear Information System (INIS)

    Robota, H.J.

    1991-01-01

    Characterization of catalysts focuses on the identification of an active site responsible for accelerating desirable chemical reactions. The identification, characterization, and selective modification of such sites is fundamental to the development of structure-function relationships. Unfortunately, this goal is far from realized in nearly all catalysts, and particularly in catalysts comprised of small supported metal particles. X-ray absorption spectroscopy (XAS) has had a dramatic effect on our understanding of supported metal particles in their resting state. However, the performance of a catalyst can not be assessed from such simple resting state measurements. Among the factors which influence catalyst performance are the exact catalyst composition, including the support and any modifiers; particle size; catalyst finishing and pretreatment conditions; pressure, composition, and temperature of the operating environment; time. Gaining an understanding of how the structure of a catalytic site can change with such an array of variables requires that we begin to develop measurement methods which are effective under chemically dynamic conditions. Ideally, it should be possible to obtain a full X-ray absorption spectrum of each element thought to have a causal relationship with observed catalyst properties. From these spectra, we can optimally extract only a relatively limited amount of information which we must then piece together with information derived from other characterization methods and intuition to arrive at a hypothetical structure of the operating catalyst. Information about crystallinity, homogeneity, and general disorder can be obtained from the Debye-Waller factor. Finally, through analogy with known compounds, the electronic structure of the active atoms can be inferred from near edge absorption features

  1. Chemically induced dynamic electron polarization. Pulse radiolysis of aqueous solutions of alcohols

    International Nuclear Information System (INIS)

    Trifunac, A.D.; Thurnauer, M.C.

    1975-01-01

    The radical pair model of chemically induced dynamic electron polarization (CIDEP) is experimentally verified. Aqueous solutions of alcohols were irradiated with 3 MeV electrons and observed with time resolved electron paramagnetic resonance (EPR) spectroscopy. Relative line intensities of the polarized EPR spectra of radicals from methanol and especially ethylene glycol, alone and in the presence of radicals from compounds containing halogens, illustrates the polarization dependence on the g-factor differences between the radical pair components. The observation of the relative polarization enhancement in the various lines of the multiline EPR spectra illustrates the polarization dependence on the hyperfine terms. Intrinsic enhancements are calculated and are shown to be proportional to the observed enhancement, showing that the radical pair model of CIDEP is qualitatively correct

  2. Study on Dynamic Alignment Technology of COIL Resonator

    International Nuclear Information System (INIS)

    Xiong, M D; Zou, X J; Guo, J H; Jia, S N; Zhang, Z B

    2006-01-01

    The performance of great power chemical oxygen-iodine laser (COIL) beam is decided mostly by resonator mirror maladjustment and environment vibration. To improve the performance of light beam, an auto-alignment device is used in COIL resonator, the device can keep COIL resonator collimating by adjusting the optical components of resonator. So the coupling model of COIL resonator is present. The multivariable self study fuzzy uncoupling arithmetic and six-dimensional micro drive technology are used to design a six-input-three-output uncoupling controller, resulting in the realization of the high precision dynamic alignment. The experiments indicate that the collimating range of this system is 8 mrad, precision is 5 urad and frequency response is 20Hz, which meet the demand of resonator alignment system

  3. Comparison of reactivity on step and terrace sites of Pd (3 3 2) surface for the dissociative adsorption of hydrogen: A quantum chemical molecular dynamics study

    International Nuclear Information System (INIS)

    Ahmed, Farouq; Nagumo, Ryo; Miura, Ryuji; Ai, Suzuki; Tsuboi, Hideyuki; Hatakeyama, Nozomu; Endou, Akira; Takaba, Hiromitsu; Kubo, Momoji; Miyamoto, Akira

    2011-01-01

    The notion of 'active sites' is fundamental to heterogeneous catalysis. However, the exact nature of the active sites, and hence the mechanism by which they act, are still largely a matter of speculation. In this study, we have presented a systematic quantum chemical molecular dynamics (QCMD) calculations for the interaction of hydrogen on different step and terrace sites of the Pd (3 3 2) surface. Finally the dissociative adsorption of hydrogen on step and terrace as well as the influence of surface hydrogen vacancy for the dissociative adsorption of hydrogen has been investigated through QCMD. This is a state-of-the-art method for calculating the interaction of atoms and molecules with metal surfaces. It is found that fully hydrogen covered (saturated) step sites can dissociate hydrogen moderately and that a monovacancy surface is suitable for significant dissociative adsorption of hydrogen. However in terrace site of the surface we have found that dissociation of hydrogen takes place only on Pd sites where the metal atom is not bound to any pre-adsorbed hydrogen atoms. Furthermore, from the molecular dynamics and electronic structure calculations, we identify a number of consequences for the interpretation and modeling of diffusion experiments demonstrating the coverage and directional dependence of atomic hydrogen diffusion on stepped palladium surface.

  4. 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.

  5. Coarse grain model for coupled thermo-mechano-chemical processes and its application to pressure-induced endothermic chemical reactions

    International Nuclear Information System (INIS)

    Antillon, Edwin; Banlusan, Kiettipong; Strachan, Alejandro

    2014-01-01

    We extend a thermally accurate model for coarse grain dynamics (Strachan and Holian 2005 Phys. Rev. Lett. 94 014301) to enable the description of stress-induced chemical reactions in the degrees of freedom internal to the mesoparticles. Similar to the breathing sphere model, we introduce an additional variable that describes the internal state of the particles and whose dynamics is governed both by an internal potential energy function and by interparticle forces. The equations of motion of these new variables are derived from a Hamiltonian and the model exhibits two desired features: total energy conservation and Galilean invariance. We use a simple model material with pairwise interactions between particles and study pressure-induced chemical reactions induced by hydrostatic and uniaxial compression. These examples demonstrate the ability of the model to capture non-trivial processes including the interplay between mechanical, thermal and chemical processes of interest in many applications. (paper)

  6. Quantitative chemical exchange saturation transfer with hyperpolarized nuclei (qHyper-CEST): sensing xenon-host exchange dynamics and binding affinities by NMR.

    Science.gov (United States)

    Kunth, M; Witte, C; Schröder, L

    2014-11-21

    The reversible binding of xenon to host molecules has found numerous applications in nuclear magnetic resonance studies. Quantitative characterization of the Xe exchange dynamics is important to understand and optimize the physico-chemical behavior of such Xe hosts, but is often challenging to achieve at low host concentrations. We have investigated a sensitive quantification technique based on chemical exchange saturation transfer with hyperpolarized nuclei, qHyper-CEST. Using simulated signals we demonstrated that qHyper-CEST yielded accurate and precise results and was robust in the presence of large amounts of noise (10%). This is of particular importance for samples with completely unknown exchange rates. Using these findings we experimentally determined the following exchange parameters for the Xe host cryptophane-A monoacid in dimethyl sulfoxide in one type of experiment: the ratio of bound and free Xe, the Xe exchange rate, the resonance frequencies of free and bound Xe, the Xe host occupancy, and the Xe binding constant. Taken together, qHyper-CEST facilitates sensitive quantification of the Xe exchange dynamics and binding to hydrophobic cavities and has the potential to analyze many different host systems or binding sites. This makes qHyper-CEST an indispensable tool for the efficient design of highly specific biosensors.

  7. Dynamics of liquids, molecules, and proteins measured with ultrafast 2D IR vibrational echo chemical exchange spectroscopy.

    Science.gov (United States)

    Fayer, M D

    2009-01-01

    A wide variety of molecular systems undergo fast structural changes under thermal equilibrium conditions. Such transformations are involved in a vast array of chemical problems. Experimentally measuring equilibrium dynamics is a challenging problem that is at the forefront of chemical research. This review describes ultrafast 2D IR vibrational echo chemical exchange experiments and applies them to several types of molecular systems. The formation and dissociation of organic solute-solvent complexes are directly observed. The dissociation times of 13 complexes, ranging from 4 ps to 140 ps, are shown to obey a relationship that depends on the complex's formation enthalpy. The rate of rotational gauche-trans isomerization around a carbon-carbon single bond is determined for a substituted ethane at room temperature in a low viscosity solvent. The results are used to obtain an approximate isomerization rate for ethane. Finally, the time dependence of a well-defined single structural transformation of a protein is measured.

  8. Global Controllability of Chemical Reactions

    OpenAIRE

    Drexler, Dániel András; Tóth, János

    2015-01-01

    Controllability of chemical reactions is an important problem in chemical engineering science. In control theory, analysis of the controllability of linear systems is well-founded, however the dynamics of chemical reactions is usually nonlinear. Global controllability properties of chemical reactions are analyzed here based on the Lie-algebra of the vector fields associated to elementary reactions. A chemical reaction is controllable almost everywhere if all the reaction rate coefficients can...

  9. Molecular dynamics of TBP and DBP studied by neutron transmission

    International Nuclear Information System (INIS)

    Salles Filho, J.B.V.; Refinetti, M.E.; Fulfaro, R.; Vinhas, L.A.

    1984-04-01

    Differences between the properties of TBP and DBP, concerning the uranium extraction processes, may be related to certain characteristics of the molecular dynamics of each compound. In order to investigate the dynamical behaviour of hydrogen in these molecules, neutron transmission of TBP and DBP has been measured as a function of neutron wavelenght in the range 4.0 - 6.0 A, at room temperature. Scattering cross sections per hydrogen atom have been obtained. From the comparison with results previously obtained for n-butanol, similar dynamical behaviour of butyl radicals in these compounds could be observed. This similarity indicates that the presence of two or three butyl radicals in butylphosphate molecules does not exert influence in the hydrogen motion of methyl and methylene groups. This suggests that the different chemical behaviour between TBP and DBP is related to the dynamics of the hydrogen directly bound to the DBP phosphate group.(Author) [pt

  10. Interaction of 3D dewetting nanodroplets on homogeneous and chemically heterogeneous substrates

    International Nuclear Information System (INIS)

    Asgari, M; Moosavi, A

    2014-01-01

    Long-time interaction of dewetting nanodroplets is investigated using a long-wave approximation method. Although three-dimensional (3D) droplets evolution dynamics exhibits qualitative behavior analogous to two-dimensional (2D) dynamics, there is an extensive quantitative difference between them. 3D dynamics is substantially faster than 2D dynamics. This can be related to the larger curvature and, as a consequence, the larger Laplace pressure difference between the droplets in 3D systems. The influence of various chemical heterogeneities on the behavior of droplets has also been studied. In the case of gradient surfaces, it is shown how the gradient direction could change the dynamics. For a chemical step located between the droplets, the dynamics is enhanced or weakened depending on the initial configuration of the system. (paper)

  11. Trajectory calculation of a trapped particle in electro-dynamic balance for study of chemical reaction of aerosol particles

    International Nuclear Information System (INIS)

    Okuma, Miho; Itou, Takahiro; Harano, Azuchi; Takarada, Takayuki; James, Davis E

    2013-01-01

    Electrodynamic balance (EDB) is a powerful tool for investigating the chemical reactions between a fine particle and gaseous species. But the EDB device alone is inadequate to match the rapid weight change of a fine particle caused by chemical reactions, because it takes a few seconds to set a fine particle at null point. The particle trajectory calculation for the trapped particle added to the EDB is thus a very useful tool for the measurement of the transient response of a particle weight change with no need to adjust the applied DC voltage to set the null point. The purpose of this study is to develop the trajectory calculation method to track the particle oscillation pattern in the EDB and examine the possibility for kinetic studies on the reaction of a single aerosol particle with gaseous species. The results demonstrated the feasibility of applying particle trajectory calculation to realize the research purpose.

  12. Journal of Chemical Sciences | Indian Academy of Sciences

    Indian Academy of Sciences (India)

    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.

  13. 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.

  14. Predicting in vivo effect levels for repeat-dose systemic toxicity using chemical, biological, kinetic and study covariates.

    Science.gov (United States)

    Truong, Lisa; Ouedraogo, Gladys; Pham, LyLy; Clouzeau, Jacques; Loisel-Joubert, Sophie; Blanchet, Delphine; Noçairi, Hicham; Setzer, Woodrow; Judson, Richard; Grulke, Chris; Mansouri, Kamel; Martin, Matthew

    2018-02-01

    In an effort to address a major challenge in chemical safety assessment, alternative approaches for characterizing systemic effect levels, a predictive model was developed. Systemic effect levels were curated from ToxRefDB, HESS-DB and COSMOS-DB from numerous study types totaling 4379 in vivo studies for 1247 chemicals. Observed systemic effects in mammalian models are a complex function of chemical dynamics, kinetics, and inter- and intra-individual variability. To address this complex problem, systemic effect levels were modeled at the study-level by leveraging study covariates (e.g., study type, strain, administration route) in addition to multiple descriptor sets, including chemical (ToxPrint, PaDEL, and Physchem), biological (ToxCast), and kinetic descriptors. Using random forest modeling with cross-validation and external validation procedures, study-level covariates alone accounted for approximately 15% of the variance reducing the root mean squared error (RMSE) from 0.96 log 10 to 0.85 log 10  mg/kg/day, providing a baseline performance metric (lower expectation of model performance). A consensus model developed using a combination of study-level covariates, chemical, biological, and kinetic descriptors explained a total of 43% of the variance with an RMSE of 0.69 log 10  mg/kg/day. A benchmark model (upper expectation of model performance) was also developed with an RMSE of 0.5 log 10  mg/kg/day by incorporating study-level covariates and the mean effect level per chemical. To achieve a representative chemical-level prediction, the minimum study-level predicted and observed effect level per chemical were compared reducing the RMSE from 1.0 to 0.73 log 10  mg/kg/day, equivalent to 87% of predictions falling within an order-of-magnitude of the observed value. Although biological descriptors did not improve model performance, the final model was enriched for biological descriptors that indicated xenobiotic metabolism gene expression, oxidative stress, and

  15. Experimental and molecular dynamics study on the inhibition performance of some nitrogen containing compounds for iron corrosion

    International Nuclear Information System (INIS)

    Khaled, K.F.

    2010-01-01

    A molecular dynamics study for the adsorption of three benzimidazole derivatives and their inhibition characteristics was studied using chemical (weight loss) and electrochemical measurements (potentiodynamic polarization and electrochemical impedance spectroscopy, EIS). Electrochemical measurements results revealed that the inhibition efficiencies increased with the concentration of inhibitors. Results obtained from weight loss, dc polarization and ac impedance measurements are in reasonably good agreement and show increased inhibitor efficiency with increasing inhibitor concentration. The molecular dynamics calculations showed that the higher the binding energy between the inhibitor and metal surface, the higher the inhibition efficiency. Also, the higher the adsorption energy, the higher the inhibition efficiency. The molecular dynamics study revealed that the benzimidazole ring as well as the side chain are the active sites in these inhibitors and they can absorb on Fe surface by donating electrons to Fe d-orbital.

  16. Consequence and Resilience Modeling for Chemical Supply Chains

    Science.gov (United States)

    Stamber, Kevin L.; Vugrin, Eric D.; Ehlen, Mark A.; Sun, Amy C.; Warren, Drake E.; Welk, Margaret E.

    2011-01-01

    The U.S. chemical sector produces more than 70,000 chemicals that are essential material inputs to critical infrastructure systems, such as the energy, public health, and food and agriculture sectors. Disruptions to the chemical sector can potentially cascade to other dependent sectors, resulting in serious national consequences. To address this concern, the U.S. Department of Homeland Security (DHS) tasked Sandia National Laboratories to develop a predictive consequence modeling and simulation capability for global chemical supply chains. This paper describes that capability , which includes a dynamic supply chain simulation platform called N_ABLE(tm). The paper also presents results from a case study that simulates the consequences of a Gulf Coast hurricane on selected segments of the U.S. chemical sector. The case study identified consequences that include impacted chemical facilities, cascading impacts to other parts of the chemical sector. and estimates of the lengths of chemical shortages and recovery . Overall. these simulation results can DHS prepare for and respond to actual disruptions.

  17. Dynamic Complexity Study of Nuclear Reactor and Process Heat Application Integration

    International Nuclear Information System (INIS)

    Taylor, J'Tia Patrice; Shropshire, David E.

    2009-01-01

    and the economic allocation of electricity and heat resources. Safety issues include changes in regulatory constraints imposed on the facilities. Modeling and analysis tools, such as System Dynamics for time dependent operational and economic issues and RELAP5 3D for chemical transient affects, are evaluated. The results of this study advance the body of knowledge toward integration of nuclear reactors and process heat applications.

  18. Molecular activation analysis for chemical speciation studies

    International Nuclear Information System (INIS)

    Chai-Chifang

    1998-01-01

    The term of Molecular Activation Analysis (MAA) refers to an activation analysis method that is able to provide information about the chemical species of elements in system of interests, though its definition has remained to be assigned. Its development is strongly stimulated by the urgent need to know the chemical species of elements, because the total concentrations are often without any meaning when assessing health or environmental risks of trace elements.In practice, the MAA is a combination of conventional instrumental or radiochemical activation analysis and physical, chemical or biochemical separation techniques. The MAA is able to play a particular role in speciation studies. However, the critical point in the MAA is that it is not permitted to change the primitive chemical species of elements in systems, or the change has to be under control; in the meantime it is not allowed to form the 'new artifact' originally not present in systems. Some practical examples of MAA for chemical species research performed recently in our laboratory will be presented as follows: Chemical species of platinum group elements in sediment; Chemical species of iodine in marine algae; Chemical species of mercury in human tissues; Chemical species of selenium in corn; Chemical species of rare earth elements in natural plant, etc. The merits and limitations of MAA will be described as well. (author)

  19. Structural and lattice dynamics studies of microcrystals by means of the Moessbauer effect spectroscopy

    International Nuclear Information System (INIS)

    Pasternak, M.

    1978-05-01

    Moessbauer studies on 129 I, 57 Fe and 119 Sn were conducted in several disordered and microscopic systems in order to investigate properties of lattice dynamics, chemical bonding and phase transitions. The project included the following studies: (1) Granular crystals of Sn embedded in tin-oxide matrix; the nature of the superconductivity transition of very small grains of tin was investigated. (2) Lattice dynamics and characterization of amorphous tin oxide obtained by condensing atoms of Sn and O 2 gas on a 77 K substrate. The hyperfine interaction and the temperature dependence of the Debye-Waller factor were essential to determine the structure of the amorphous tin oxide. (3) The nature of the chemical bond of the alkaly halides ionic crystals and molecules; molecules of Li, Na, K, Rb and Cs iodides were trapped in agron matrices, and the isomer-shift values were obtained from absorption spectra. (4) Binding of single iron and tin atoms to CH 4 , NH 3 , H 2 and C 6 H 6 molecules, with samples at low temperatures between 2 and 77 K; conclusions were derived regarding the cryochemistry of these systems, as related to fundamental problems of catalysis, chemisorption and ''cracking'' of organic molecules

  20. Two-color QCD with non-zero chiral chemical potential

    Energy Technology Data Exchange (ETDEWEB)

    Braguta, V.V. [Institute for High Energy Physics NRC “Kurchatov Institute' ,142281 Protvino (Russian Federation); Far Eastern Federal University, School of Biomedicine,690950 Vladivostok (Russian Federation); Goy, V.A. [Far Eastern Federal University, School of Natural Sciences,690950 Vladivostok (Russian Federation); Ilgenfritz, E.M. [Joint Institute for Nuclear Research,BLTP, 141980 Dubna (Russian Federation); Kotov, A.Yu. [Institute of Theoretical and Experimental Physics,117259 Moscow (Russian Federation); Molochkov, A.V. [Far Eastern Federal University, School of Biomedicine,690950 Vladivostok (Russian Federation); Müller-Preussker, M.; Petersson, B. [Humboldt-Universität zu Berlin, Institut für Physik,12489 Berlin (Germany)

    2015-06-16

    The phase diagram of two-color QCD with non-zero chiral chemical potential is studied by means of lattice simulation. We focus on the influence of a chiral chemical potential on the confinement/deconfinement phase transition and the breaking/restoration of chiral symmetry. The simulation is carried out with dynamical staggered fermions without rooting. The dependences of the Polyakov loop, the chiral condensate and the corresponding susceptibilities on the chiral chemical potential and the temperature are presented. The critical temperature is observed to increase with increasing chiral chemical potential.

  1. Rayleigh-type parametric chemical oscillation

    Energy Technology Data Exchange (ETDEWEB)

    Ghosh, Shyamolina; Ray, Deb Shankar, E-mail: pcdsr@iacs.res.in [Indian Association for the Cultivation of Science, Jadavpur, Kolkata 700032 (India)

    2015-09-28

    We consider a nonlinear chemical dynamical system of two phase space variables in a stable steady state. When the system is driven by a time-dependent sinusoidal forcing of a suitable scaling parameter at a frequency twice the output frequency and the strength of perturbation exceeds a threshold, the system undergoes sustained Rayleigh-type periodic oscillation, wellknown for parametric oscillation in pipe organs and distinct from the usual forced quasiperiodic oscillation of a damped nonlinear system where the system is oscillatory even in absence of any external forcing. Our theoretical analysis of the parametric chemical oscillation is corroborated by full numerical simulation of two well known models of chemical dynamics, chlorite-iodine-malonic acid and iodine-clock reactions.

  2. Rayleigh-type parametric chemical oscillation.

    Science.gov (United States)

    Ghosh, Shyamolina; Ray, Deb Shankar

    2015-09-28

    We consider a nonlinear chemical dynamical system of two phase space variables in a stable steady state. When the system is driven by a time-dependent sinusoidal forcing of a suitable scaling parameter at a frequency twice the output frequency and the strength of perturbation exceeds a threshold, the system undergoes sustained Rayleigh-type periodic oscillation, wellknown for parametric oscillation in pipe organs and distinct from the usual forced quasiperiodic oscillation of a damped nonlinear system where the system is oscillatory even in absence of any external forcing. Our theoretical analysis of the parametric chemical oscillation is corroborated by full numerical simulation of two well known models of chemical dynamics, chlorite-iodine-malonic acid and iodine-clock reactions.

  3. Structural investigation of water-acetonitrile mixtures: An ab initio, molecular dynamics and X-ray diffraction study

    International Nuclear Information System (INIS)

    Bako, Imre; Megyes, Tuende; Palinkas, Gabor

    2005-01-01

    In this work, we present a study on water-acetonitrile (AN) mixtures by molecular dynamics ab initio and X-ray diffraction techniques. Comparison of the experimental total G(r) functions of the mixtures with the results of molecular dynamics simulation shows an overall good agreement. The properties of hydrogen bonded clusters (water clusters, and water-AN clusters) in these mixtures have been determined. Two different types of AN-water dimers were identified by ab initio quantum chemical calculation. One of these structures proved to be a true H-bonded dimer and the other a dipole bound dimer

  4. Dynamical equilibration in strongly-interacting parton-hadron matter

    Directory of Open Access Journals (Sweden)

    Gorenstein M.

    2011-04-01

    Full Text Available We study the kinetic and chemical equilibration in 'infinite' parton-hadron matter within the Parton-Hadron-String Dynamics transport approach, which is based on a dynamical quasiparticle model for partons matched to reproduce lattice-QCD results – including the partonic equation of state – in thermodynamic equilibrium. The 'infinite' matter is simulated within a cubic box with periodic boundary conditions initialized at different baryon density (or chemical potential and energy density. The transition from initially pure partonic matter to hadronic degrees of freedom (or vice versa occurs dynamically by interactions. Different thermody-namical distributions of the strongly-interacting quark-gluon plasma (sQGP are addressed and discussed.

  5. Mechanical properties of moso bamboo treated with chemical agents

    Science.gov (United States)

    Benhua Fei; Zhijia Liu; Zehui Jiang; Zhiyong Cai

    2013-01-01

    Bamboo is a type of biomass material and has great potential as a bioenergy resource for the future in China. Surface chemical and thermal–mechanical behavior play an important role in the manufacturing process of bamboo composites and pellets. In this study, moso bamboo was treated by sodium hydrate solution and acetic acid solution. Surface chemical and dynamic...

  6. Switching dynamics in reaction networks induced by molecular discreteness

    International Nuclear Information System (INIS)

    Togashi, Yuichi; Kaneko, Kunihiko

    2007-01-01

    To study the fluctuations and dynamics in chemical reaction processes, stochastic differential equations based on the rate equation involving chemical concentrations are often adopted. When the number of molecules is very small, however, the discreteness in the number of molecules cannot be neglected since the number of molecules must be an integer. This discreteness can be important in biochemical reactions, where the total number of molecules is not significantly larger than the number of chemical species. To elucidate the effects of such discreteness, we study autocatalytic reaction systems comprising several chemical species through stochastic particle simulations. The generation of novel states is observed; it is caused by the extinction of some molecular species due to the discreteness in their number. We demonstrate that the reaction dynamics are switched by a single molecule, which leads to the reconstruction of the acting network structure. We also show the strong dependence of the chemical concentrations on the system size, which is caused by transitions to discreteness-induced novel states

  7. 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.

  8. A Simplified Approach to Risk Assessment Based on System Dynamics: An Industrial Case Study.

    Science.gov (United States)

    Garbolino, Emmanuel; Chery, Jean-Pierre; Guarnieri, Franck

    2016-01-01

    Seveso plants are complex sociotechnical systems, which makes it appropriate to support any risk assessment with a model of the system. However, more often than not, this step is only partially addressed, simplified, or avoided in safety reports. At the same time, investigations have shown that the complexity of industrial systems is frequently a factor in accidents, due to interactions between their technical, human, and organizational dimensions. In order to handle both this complexity and changes in the system over time, this article proposes an original and simplified qualitative risk evaluation method based on the system dynamics theory developed by Forrester in the early 1960s. The methodology supports the development of a dynamic risk assessment framework dedicated to industrial activities. It consists of 10 complementary steps grouped into two main activities: system dynamics modeling of the sociotechnical system and risk analysis. This system dynamics risk analysis is applied to a case study of a chemical plant and provides a way to assess the technological and organizational components of safety. © 2016 Society for Risk Analysis.

  9. 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

  10. Partial chemical equilibrium in fluid dynamics

    International Nuclear Information System (INIS)

    Ramshaw, J.D.

    1980-01-01

    An analysis is given for the flow of a multicomponent fluid in which an arbitrary number of chemical reactions may occur, some of which are in equilibrium while the others proceed kinetically. The primitive equations describing this situation are inconvenient to use because the progress rates omega-dot/sub s/ for the equilibrium reactions are determined implicitly by the associated equilibrium constraint conditions. Two alternative equivalent equation systems that are more pleasant to deal with are derived. In the first system, the omega-dot/sub s/ are eliminated by replacing the transport equations for the chemical species involved in the equilibrium reactions with transport equations for the basic components of which these species are composed. The second system retains the usual species transport equations, but eliminates the nonlinear algebraic equilibrium constraint conditions by deriving an explicit expression for the omega-dot/sub s/. Both systems are specialized to the case of an ideal gas mixture. Considerations involved in solving these equation systems numerically are discussed briefly

  11. 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.

  12. Co-exposure with fullerene may strengthen health effects of organic industrial chemicals.

    Directory of Open Access Journals (Sweden)

    Maili Lehto

    Full Text Available In vitro toxicological studies together with atomistic molecular dynamics simulations show that occupational co-exposure with C60 fullerene may strengthen the health effects of organic industrial chemicals. The chemicals studied are acetophenone, benzaldehyde, benzyl alcohol, m-cresol, and toluene which can be used with fullerene as reagents or solvents in industrial processes. Potential co-exposure scenarios include a fullerene dust and organic chemical vapor, or a fullerene solution aerosolized in workplace air. Unfiltered and filtered mixtures of C60 and organic chemicals represent different co-exposure scenarios in in vitro studies where acute cytotoxicity and immunotoxicity of C60 and organic chemicals are tested together and alone by using human THP-1-derived macrophages. Statistically significant co-effects are observed for an unfiltered mixture of benzaldehyde and C60 that is more cytotoxic than benzaldehyde alone, and for a filtered mixture of m-cresol and C60 that is slightly less cytotoxic than m-cresol. Hydrophobicity of chemicals correlates with co-effects when secretion of pro-inflammatory cytokines IL-1β and TNF-α is considered. Complementary atomistic molecular dynamics simulations reveal that C60 co-aggregates with all chemicals in aqueous environment. Stable aggregates have a fullerene-rich core and a chemical-rich surface layer, and while essentially all C60 molecules aggregate together, a portion of organic molecules remains in water.

  13. Pulse-density modulation control of chemical oscillation far from equilibrium in a droplet open-reactor system.

    Science.gov (United States)

    Sugiura, Haruka; Ito, Manami; Okuaki, Tomoya; Mori, Yoshihito; Kitahata, Hiroyuki; Takinoue, Masahiro

    2016-01-20

    The design, construction and control of artificial self-organized systems modelled on dynamical behaviours of living systems are important issues in biologically inspired engineering. Such systems are usually based on complex reaction dynamics far from equilibrium; therefore, the control of non-equilibrium conditions is required. Here we report a droplet open-reactor system, based on droplet fusion and fission, that achieves dynamical control over chemical fluxes into/out of the reactor for chemical reactions far from equilibrium. We mathematically reveal that the control mechanism is formulated as pulse-density modulation control of the fusion-fission timing. We produce the droplet open-reactor system using microfluidic technologies and then perform external control and autonomous feedback control over autocatalytic chemical oscillation reactions far from equilibrium. We believe that this system will be valuable for the dynamical control over self-organized phenomena far from equilibrium in chemical and biomedical studies.

  14. Characterization of chemical interactions during chemical mechanical polishing (CMP) of copper

    Science.gov (United States)

    Lee, Seung-Mahn

    2003-10-01

    Chemical mechanical polishing (CMP) has received much attention as an unique technique to provide a wafer level planarization in semiconductor manufacturing. However, despite the extensive use of CMP, it still remains one of the least understood areas in semiconductor processing. The lack of the fundamental understanding is a significant barrier to further advancements in CMP technology. One critical aspect of metal CMP is the formation of a thin surface layer on the metal surface. The formation and removal of this layer controls all the aspects of the CMP process, including removal rate, surface finish, etc. In this dissertation, we focus on the characterization of the formation and removal of the thin surface layer on the copper surface. The formation dynamics was investigated using static and dynamic electrochemical techniques, including potentiodynamic scans and chronoamperometry. The results were validated using XPS measurements. The mechanical properties of the surface layer were investigated using nanoindentation measurements. The electrochemical investigation showed that the thickness of the surface layer is controlled by the chemicals such as an oxidizer (hydrogen peroxide), a corrosion inhibitor (benzotriazole), a complexing agent (citric acid), and their concentrations. The dynamic electrochemical measurements indicated that the initial layer formation kinetics is unaffected by the corrosion inhibitors. The passivation due to the corrosion inhibitor becomes important only on large time scales (>200 millisecond). The porosity and the density of the chemically modified surface layer can be affected by additives of other chemicals such as citric acid. An optimum density of the surface layer is required for high polishing rate while at the same time maintaining a high degree of surface finish. Nanoindentation measurements indicated that the mechanical properties of the surface layer are strongly dependent on the chemical additives in the slurry. The CMP

  15. Simulating chemical systems : MPI and GPU parallelization of novel SD algorithms

    NARCIS (Netherlands)

    Goga, N.

    Molecular dynamics is used for simulating chemical systems with the goal of studying a large range of phenomena starting from cell structures to the design of new materials, drugs, etc. A very important component of molecular dynamics is the use of well-suited atomistic and molecular modelling of

  16. Independent alignment of RNA for dynamic studies using residual dipolar couplings

    Energy Technology Data Exchange (ETDEWEB)

    Bardaro, Michael F.; Varani, Gabriele, E-mail: varani@chem.washington.edu [University of Washington, Department of Chemistry (United States)

    2012-09-15

    Molecular motion and dynamics play an essential role in the biological function of many RNAs. An important source of information on biomolecular motion can be found in residual dipolar couplings which contain dynamics information over the entire ms-ps timescale. However, these methods are not fully applicable to RNA because nucleic acid molecules tend to align in a highly collinear manner in different alignment media. As a consequence, information on dynamics that can be obtained with this method is limited. In order to overcome this limitation, we have generated a chimeric RNA containing both the wild type TAR RNA, the target of our investigation of dynamics, as well as the binding site for U1A protein. When U1A protein was bound to the portion of the chimeric RNA containing its binding site, we obtained independent alignment of TAR by exploiting the physical chemical characteristics of this protein. This technique can allow the extraction of new information on RNA dynamics, which is particularly important for time scales not covered by relaxation methods where important RNA motions occur.

  17. Studying Dynamics in Business Networks

    DEFF Research Database (Denmark)

    Andersen, Poul Houman; Anderson, Helen; Havila, Virpi

    1998-01-01

    This paper develops a theory on network dynamics using the concepts of role and position from sociological theory. Moreover, the theory is further tested using case studies from Denmark and Finland......This paper develops a theory on network dynamics using the concepts of role and position from sociological theory. Moreover, the theory is further tested using case studies from Denmark and Finland...

  18. Butschli Dynamic Droplet System

    DEFF Research Database (Denmark)

    Armstrong, R.; Hanczyc, M.

    2013-01-01

    Dynamical oil-water systems such as droplets display lifelike properties and may lend themselves to chemical programming to perform useful work, specifically with respect to the built environment. We present Butschli water-in-oil droplets as a model for further investigation into the development...... reconstructed the Butschli system and observed its life span under a light microscope, observing chemical patterns and droplet behaviors in nearly three hundred replicate experiments. Self-organizing patterns were observed, and during this dynamic, embodied phase the droplets provided a means of introducing...... temporal and spatial order in the system with the potential for chemical programmability. The authors propose that the discrete formation of dynamic droplets, characterized by their lifelike behavior patterns, during a variable window of time (from 30 s to 30 min after the addition of alkaline water...

  19. Contribution to chemical-mineralogical study of carbonatites

    International Nuclear Information System (INIS)

    Costa, M.Q. da; Lima, W.N. de; Correa, S.L.A.

    1982-01-01

    A preliminary chemical-mineralogical study of carbonatites from Jacupiranga (SP,Brazil) and Alto Pinheiros (SC,Brazil) enabled not only to ratify hypotheses previously described by Brazilian researchers but also made clear certain aspects related to the geochemistry of carbonatites concerning their occurrence, the probable genesis of these species and their chemical and mineralogical characteristics.(Author) [pt

  20. 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,...

  1. Strangeness chemical equilibration in a quark-gluon plasma

    International Nuclear Information System (INIS)

    Letessier, Jean; Rafelski, Johann

    2007-01-01

    We study, in the dynamically evolving quark-gluon plasma (QGP) fireball formed in relativistic heavy ion collisions at the BNL Relativistic Heavy Ion Collider (RHIC) and CERN Large Hadron Collider (LHC), the growth of strangeness yield toward and beyond the chemical equilibrium. We account for the contribution of the direct strangeness production and evaluate the thermal-QCD strangeness production mechanisms. The specific yield of strangeness per entropy, s/S, is the primary target variable. We explore the effect of collision impact parameter, i.e., fireball size, on kinetic strangeness chemical equilibration in QGP. Insights gained in studying the RHIC data with regard to the dynamics of the fireball are applied to the study of strangeness production at the LHC. We use these results and consider the strange hadron relative particle yields at RHIC and LHC in a systematic fashion. We consider both the dependence on s/S and the direct dependence on the participant number

  2. Quantum mechanical tunneling in chemical physics

    CERN Document Server

    Nakamura, Hiroki

    2016-01-01

    Quantum mechanical tunneling plays important roles in a wide range of natural sciences, from nuclear and solid-state physics to proton transfer and chemical reactions in chemistry and biology. Responding to the need for further understanding of multidimensional tunneling, the authors have recently developed practical methods that can be applied to multidimensional systems. Quantum Mechanical Tunneling in Chemical Physics presents basic theories, as well as original ones developed by the authors. It also provides methodologies and numerical applications to real molecular systems. The book offers information so readers can understand the basic concepts and dynamics of multidimensional tunneling phenomena and use the described methods for various molecular spectroscopy and chemical dynamics problems. The text focuses on three tunneling phenomena: (1) energy splitting, or tunneling splitting, in symmetric double well potential, (2) decay of metastable state through tunneling, and (3) tunneling effects in chemical...

  3. Biofiltration of airborne VOCs with green wall systems-Microbial and chemical dynamics.

    Science.gov (United States)

    Mikkonen, A; Li, T; Vesala, M; Saarenheimo, J; Ahonen, V; Kärenlampi, S; Blande, J D; Tiirola, M; Tervahauta, A

    2018-05-06

    Botanical air filtration is a promising technology for reducing indoor air contaminants, but the underlying mechanisms need better understanding. Here, we made a set of chamber fumigation experiments of up to 16 weeks of duration, to study the filtration efficiencies for seven volatile organic compounds (VOCs; decane, toluene, 2-ethylhexanol, α-pinene, octane, benzene, and xylene) and to monitor microbial dynamics in simulated green wall systems. Biofiltration functioned on sub-ppm VOC levels without concentration-dependence. Airflow through the growth medium was needed for efficient removal of chemically diverse VOCs, and the use of optimized commercial growth medium further improved the efficiency compared with soil and Leca granules. Experimental green wall simulations using these components were immediately effective, indicating that initial VOC removal was largely abiotic. Golden pothos plants had a small additional positive impact on VOC filtration and bacterial diversity in the green wall system. Proteobacteria dominated the microbiota of rhizosphere and irrigation water. Airborne VOCs shaped the microbial communities, enriching potential VOC-utilizing bacteria (especially Nevskiaceae and Patulibacteraceae) in the irrigation water, where much of the VOC degradation capacity of the biofiltration systems resided. These results clearly show the benefits of active air circulation and optimized growth media in modern green wall systems. © 2018 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

  4. Ab Initio Studies of Shock-Induced Chemical Reactions of Inter-Metallics

    Science.gov (United States)

    Zaharieva, Roussislava; Hanagud, Sathya

    2009-06-01

    Shock-induced and shock assisted chemical reactions of intermetallic mixtures are studied by many researchers, using both experimental and theoretical techniques. The theoretical studies are primarily at continuum scales. The model frameworks include mixture theories and meso-scale models of grains of porous mixtures. The reaction models vary from equilibrium thermodynamic model to several non-equilibrium thermodynamic models. The shock-effects are primarily studied using appropriate conservation equations and numerical techniques to integrate the equations. All these models require material constants from experiments and estimates of transition states. Thus, the objective of this paper is to present studies based on ab initio techniques. The ab inito studies, to date, use ab inito molecular dynamics. This paper presents a study that uses shock pressures, and associated temperatures as starting variables. Then intermetallic mixtures are modeled as slabs. The required shock stresses are created by straining the lattice. Then, ab initio binding energy calculations are used to examine the stability of the reactions. Binding energies are obtained for different strain components super imposed on uniform compression and finite temperatures. Then, vibrational frequencies and nudge elastic band techniques are used to study reactivity and transition states. Examples include Ni and Al.

  5. Study on the Flare Load Estimation of the Deethanizer using Dynamic Simulation

    Energy Technology Data Exchange (ETDEWEB)

    Park, Kyungtae; Won, Wangyun [GS EC, Seoul (Korea, Republic of); Shin, Dongil [Myongji University, Yongin (Korea, Republic of)

    2014-10-15

    A flare system is a very important system that crucially affects on the process safety in chemical plants. If a flare system is designed too small, it cannot prevent catastrophic accidents of a chemical plant. On the other hand, if a flare system is designed too large, it will waste resources. Therefore, reasonable relief load estimation has been a crucial issue in the industry. American Petroleum Institute (API) suggests basic guidelines for relief load estimation, and a lot of engineering companies have developed their own relief load estimation methods that use an unbalanced heat and material method. However, these methods have to involve lots of conservative assumptions that lead to an overestimation of relief loads. In this study, the new design procedure for a flare system based on dynamic simulation was proposed in order to avoid the overestimation of relief loads. The relief load of a deethanizer process was tested to verify the performance of the proposed design procedure.

  6. Dynamic Complexity Study of Nuclear Reactor and Process Heat Application Integration

    Energy Technology Data Exchange (ETDEWEB)

    J' Tia Patrice Taylor; David E. Shropshire

    2009-09-01

    system and the economic allocation of electricity and heat resources. Safety issues include changes in regulatory constraints imposed on the facilities. Modeling and analysis tools, such as System Dynamics for time dependent operational and economic issues and RELAP5 3D for chemical transient affects, are evaluated. The results of this study advance the body of knowledge toward integration of nuclear reactors and process heat applications.

  7. Effects of ion-neutral chemical reactions on dynamics of lightning-induced electric field

    International Nuclear Information System (INIS)

    Hiraki, Yasutaka

    2009-01-01

    Secondary lightning phenomena in the upper atmosphere called sprites attract interest from the viewpoint of atomic-molecular and plasma physics. Lightning-induced electric field accelerates the ionospheric electrons up to tens of electron-volts, inducing electrical breakdown as well as strong optical emissions, through electron impact ionization of molecules. A large-scale structure of sprites is constructed by collective dynamics of filamentary streamer discharges in a rarified gas, which in turn is controlled by the distribution of the background electric field. In this paper, we firstly reanalyze the relationship between quasi-static field formation and local ion chemistry with first-order perturbation techniques. Secondly, we investigate with a full ion chemical model the effects of electron attachment to oxygen molecules on its density in moderate cases of undervoltage lightning electric fields rather than the cases of intense ionization in streamers. We estimate the minimum values that are provided by the chemical balance with electron detachment from negative ions. We also investigate the recovery timescale of the electron density and find that the scale (≥1 s) is occasionally much larger than the interval of each lightning stroke (∼10 ms). We suggest that the subsequent sprite event as well as the field formation could be well affected by the ghost of the primary event. We discuss further the negative ion chemistry triggered by electron attachment in the nighttime mesosphere.

  8. The Conceptual Change Approach to Teaching Chemical Equilibrium

    Science.gov (United States)

    Canpolat, Nurtac; Pinarbasi, Tacettin; Bayrakceken, Samih; Geban, Omer

    2006-01-01

    This study investigates the effect of a conceptual change approach over traditional instruction on students' understanding of chemical equilibrium concepts (e.g. dynamic nature of equilibrium, definition of equilibrium constant, heterogeneous equilibrium, qualitative interpreting of equilibrium constant, changing the reaction conditions). This…

  9. Time-resolved X-ray photoelectron spectroscopy techniques for the study of interfacial charge dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Neppl, Stefan, E-mail: sneppl@lbl.gov; Gessner, Oliver

    2015-04-15

    Highlights: • Ultrafast interfacial charge transfer is probed with atomic site specificity. • Femtosecond X-ray photoelectron spectroscopy using a free electron laser. • Efficient and flexible picosecond X-ray photoelectron pump–probe scheme using synchrotron radiation. - Abstract: X-ray photoelectron spectroscopy (XPS) is one of the most powerful techniques to quantitatively analyze the chemical composition and electronic structure of surfaces and interfaces in a non-destructive fashion. Extending this technique into the time domain has the exciting potential to shed new light on electronic and chemical dynamics at surfaces by revealing transient charge configurations with element- and site-specificity. Here, we describe prospects and challenges that are associated with the implementation of picosecond and femtosecond time-resolved X-ray photoelectron spectroscopy at third-generation synchrotrons and X-ray free-electron lasers, respectively. In particular, we discuss a series of laser-pump/X-ray-probe photoemission experiments performed on semiconductor surfaces, molecule-semiconductor interfaces, and films of semiconductor nanoparticles that demonstrate the high sensitivity of time-resolved XPS to light-induced charge carrier generation, diffusion and recombination within the space charge layers of these materials. Employing the showcase example of photo-induced electronic dynamics in a dye-sensitized semiconductor system, we highlight the unique possibility to probe heterogeneous charge transfer dynamics from both sides of an interface, i.e., from the perspective of the molecular electron donor and the semiconductor acceptor, simultaneously. Such capabilities will be crucial to improve our microscopic understanding of interfacial charge redistribution and associated chemical dynamics, which are at the heart of emerging energy conversion, solar fuel generation, and energy storage technologies.

  10. Kinetic calorimetry in the study of the mechanism of low-temperature chemical reactions

    Science.gov (United States)

    Barkalov, I. M.; Kiryukhin, D. P.

    schemes are described [1-5]. However, despite the high working characteristics of modern calorimeters (Perkin-Elmer, Du Pont, LKB, etc.), all of them have one principal disadvantage: a cell with a sample is placed in them at room temperature. In cryochemical investigation, when the sample has metastable formations, the loading is made `from nitrogen to nitrogen', i.e. the sample prepared at 77 K should be loaded into a calorimeter at 77 K. Besides, the existing installations do not allow measurements at the temperatures Cryochemistry and Radiation Chemistry at the Institute of Chemical Physics in Chernogolovka has created original calorimetric techniques which allow: (1) the carrying out phase analysis and the determination of the main thermodynamic characteristic of individual substances and complicated systems in the temperature range 5 300 K. Sample loading can be conducted at 77 K that allows us to study the systems containing: tetrafiuoroethylene, hexafluoropropylene, ethylene, carbon monoxide, nitrogen, methane, hydrogen, oxygen, ozone, formaldehyde and many other gaseous substances; (2) the study of the dynamics of chemical reactions and to measure the main kinetic parameters of the processes-the elementary rate constants and the activation energies. The experiment can be conducted both under direct action of radiation and UV light and in the post-effect mode [5,6].

  11. Imaging Molecular Motion: Femtosecond X-Ray Scattering of an Electrocyclic Chemical Reaction

    Science.gov (United States)

    Minitti, M. P.; Budarz, J. M.; Kirrander, A.; Robinson, J. S.; Ratner, D.; Lane, T. J.; Zhu, D.; Glownia, J. M.; Kozina, M.; Lemke, H. T.; Sikorski, M.; Feng, Y.; Nelson, S.; Saita, K.; Stankus, B.; Northey, T.; Hastings, J. B.; Weber, P. M.

    2015-06-01

    Structural rearrangements within single molecules occur on ultrafast time scales. Many aspects of molecular dynamics, such as the energy flow through excited states, have been studied using spectroscopic techniques, yet the goal to watch molecules evolve their geometrical structure in real time remains challenging. By mapping nuclear motions using femtosecond x-ray pulses, we have created real-space representations of the evolving dynamics during a well-known chemical reaction and show a series of time-sorted structural snapshots produced by ultrafast time-resolved hard x-ray scattering. A computational analysis optimally matches the series of scattering patterns produced by the x rays to a multitude of potential reaction paths. In so doing, we have made a critical step toward the goal of viewing chemical reactions on femtosecond time scales, opening a new direction in studies of ultrafast chemical reactions in the gas phase.

  12. Molecular dynamics simulation of chemical sputtering of hydrogen atom on layer structured graphite

    International Nuclear Information System (INIS)

    Ito, A.; Wang, Y.; Irle, S.; Morokuma, K.; Nakamura, H.

    2008-10-01

    Chemical sputtering of hydrogen atom on graphite was simulated using molecular dynamics. Especially, the layer structure of the graphite was maintained by interlayer intermolecular interaction. Three kinds of graphite surfaces, flat (0 0 0 1) surface, armchair (1 1 2-bar 0) surface and zigzag (1 0 1-bar 0) surface, are dealt with as targets of hydrogen atom bombardment. In the case of the flat surface, graphene layers were peeled off one by one and yielded molecules had chain structures. On the other hand, C 2 H 2 and H 2 are dominant yielded molecules on the armchair and zigzag surfaces, respectively. In addition, the interaction of a single hydrogen isotope on a single graphene is investigated. Adsorption, reflection and penetration rates are obtained as functions of incident energy and explain hydrogen retention on layered graphite. (author)

  13. Structure and dynamics of solutions

    CERN Document Server

    Ohtaki, H

    2013-01-01

    Recent advances in the study of structural and dynamic properties of solutions have provided a molecular picture of solute-solvent interactions. Although the study of thermodynamic as well as electronic properties of solutions have played a role in the development of research on the rate and mechanism of chemical reactions, such macroscopic and microscopic properties are insufficient for a deeper understanding of fast chemical and biological reactions. In order to fill the gap between the two extremes, it is necessary to know how molecules are arranged in solution and how they change their pos

  14. Dynamics of curved fronts

    CERN Document Server

    Pelce, Pierre

    1989-01-01

    In recent years, much progress has been made in the understanding of interface dynamics of various systems: hydrodynamics, crystal growth, chemical reactions, and combustion. Dynamics of Curved Fronts is an important contribution to this field and will be an indispensable reference work for researchers and graduate students in physics, applied mathematics, and chemical engineering. The book consist of a 100 page introduction by the editor and 33 seminal articles from various disciplines.

  15. 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.

  16. Creating and maintaining chemical artificial life by robotic symbiosis

    DEFF Research Database (Denmark)

    Hanczyc, Martin M.; Parrilla, Juan M.; Nicholson, Arwen

    2015-01-01

    We present a robotic platform based on the open source RepRap 3D printer that can print and maintain chemical artificial life in the form of a dynamic, chemical droplet. The robot uses computer vision, a self-organizing map, and a learning program to automatically categorize the behavior of the d......We present a robotic platform based on the open source RepRap 3D printer that can print and maintain chemical artificial life in the form of a dynamic, chemical droplet. The robot uses computer vision, a self-organizing map, and a learning program to automatically categorize the behavior...... confluence of chemical, artificial intelligence, and robotic approaches to artificial life....

  17. Creating and Maintaining Chemical Artificial Life by Robotic Symbiosis

    DEFF Research Database (Denmark)

    Hanczyc, Martin; Parrilla, Juan M.; Nicholson, Arwen

    2015-01-01

    We present a robotic platform based on the open source RepRap 3D printer that can print and maintain chemical artificial life in the form of a dynamic, chemical droplet. The robot uses computer vision, a self-organizing map, and a learning program to automatically categorize the behavior of the d......We present a robotic platform based on the open source RepRap 3D printer that can print and maintain chemical artificial life in the form of a dynamic, chemical droplet. The robot uses computer vision, a self-organizing map, and a learning program to automatically categorize the behavior...... confluence of chemical, artificial intelligence, and robotic approaches to artificial life....

  18. Structure, Reactivity and Dynamics

    Indian Academy of Sciences (India)

    Understanding structure, reactivity and dynamics is the core issue in chemical ... functional theory (DFT) calculations, molecular dynamics (MD) simulations, light- ... between water and protein oxygen atoms, the superionic conductors which ...

  19. Dynamical, structural and chemical heterogeneities in a binary metallic glass-forming liquid

    Science.gov (United States)

    Puosi, F.; Jakse, N.; Pasturel, A.

    2018-04-01

    As it approaches the glass transition, particle motion in liquids becomes highly heterogeneous and regions with virtually no mobility coexist with liquid-like domains. This complex dynamic is believed to be responsible for different phenomena including non-exponential relaxation and the breakdown of the Stokes-Einstein relation. Understanding the relationships between dynamical heterogeneities and local structure in metallic liquids and glasses is a major scientific challenge. Here we use classical molecular dynamics simulations to study the atomic dynamics and microscopic structure of Cu50Zr50 alloy in the supercooling regime. Dynamical heterogeneities are identified via an isoconfigurational analysis. We demonstrate the transition from isolated to clustering low mobility with decreasing temperature. These slow clusters, whose sizes grow upon cooling, are also associated with concentration fluctuations, characterized by a Zr-enriched phase, with a composition CuZr2 . In addition, a structural analysis of slow clusters based on Voronoi tessellation evidences an increase with respect of the bulk system of the fraction of Cu atoms having a local icosahedral order. These results are in agreement with the consolidated scenario of the relevant role played by icosahedral order in the dynamic slowing-down in supercooled metal alloys.

  20. Stochastic dynamics and irreversibility

    CERN Document Server

    Tomé, Tânia

    2015-01-01

    This textbook presents an exposition of stochastic dynamics and irreversibility. It comprises the principles of probability theory and the stochastic dynamics in continuous spaces, described by Langevin and Fokker-Planck equations, and in discrete spaces, described by Markov chains and master equations. Special concern is given to the study of irreversibility, both in systems that evolve to equilibrium and in nonequilibrium stationary states. Attention is also given to the study of models displaying phase transitions and critical phenomema both in thermodynamic equilibrium and out of equilibrium. These models include the linear Glauber model, the Glauber-Ising model, lattice models with absorbing states such as the contact process and those used in population dynamic and spreading of epidemic, probabilistic cellular automata, reaction-diffusion processes, random sequential adsorption and dynamic percolation. A stochastic approach to chemical reaction is also presented.The textbook is intended for students of ...

  1. A swinging seesaw as a novel model mechanism for time-dependent hormesis under dose-dependent stimulatory and inhibitory effects: A case study on the toxicity of antibacterial chemicals to Aliivibrio fischeri.

    Science.gov (United States)

    Sun, Haoyu; Calabrese, Edward J; Zheng, Min; Wang, Dali; Pan, Yongzheng; Lin, Zhifen; Liu, Ying

    2018-08-01

    Hormesis occurs frequently in broadly ranging biological areas (e.g. plant biology, microbiology, biogerontology), toxicology, pharmacology and medicine. While numerous mechanisms (e.g. receptor and pathway mediated pathway responses) account for stimulatory and inhibitory features of hormetic dose responses, the vast majority emphasizes the inclusion of many doses but only one timepoint or use of a single optimized dose that is assessed over a broad range of timepoints. In this paper, a toxicity study was designed using a large number of properly spaced doses with responses determined over a large number of timepoints, which could help us reveal the underlying mechanism of hormesis. We present the results of a dose-time-response study on hormesis using five antibacterial chemicals on the bioluminescence of Aliivibrio fischeri, measuring expression of protein mRNA based on quorum sensing, simulating bioluminescent reaction and analyzing toxic actions of test chemicals. The findings show dose-time-dependent responses conforming to the hormetic dose-response model, while revealing unique response dynamics between agent induced stimulatory and inhibitory effects within bacterial growth phase dynamics. These dynamic dose-time features reveal a type of biological seesaw model that integrates stimulatory and inhibitory responses within unique growth phase, dose and time features, which has faultlessly explained the time-dependent hormetic phenomenon induced by five antibacterial chemicals (characterized by low-dose stimulation and high-dose inhibition). This study offers advances in understanding cellular dynamics, the biological integration of diverse and opposing responses and their role in evolutionary adaptive strategies to chemicals, which can provide new insight into the mechanistic investigation of hormesis. Copyright © 2018 Elsevier Ltd. All rights reserved.

  2. Photochemical dynamics of surface oriented molecules

    International Nuclear Information System (INIS)

    Ho, W.

    1992-01-01

    The period 8/01/91-7/31/92 is the first year of a new project titled ''Photochemical Dynamics of Surface Oriented Molecules'', initiated with DOE Support. The main objective of this project is to understand the dynamics of elementary chemical reactions by studying photochemical dynamics of surface-oriented molecules. In addition, the mechanisms of photon-surface interactions need to be elucidated. The strategy is to carry out experiments to measure the translational energy distribution, as a function of the angle from the surface normal, of the photoproducts by time-of-flight (TOF) technique by varying the photon wavelength, intensity, polarization, and pulse duration. By choosing adsorbates with different bonding configuration, the effects of adsorbate orientation on surface photochemical dynamics can be studied

  3. Dynamic Monte-Carlo modeling of hydrogen retention and chemical erosion from Tore Supra deposits

    International Nuclear Information System (INIS)

    Rai, A.; Schneider, R.; Warrier, M.; Roubin, P.; Martin, C.

    2009-01-01

    A multi-scale model has been developed to study the hydrogen retention [A. Rai, R. Schneider, M. Warrier, J. Nucl. Mater. 374 (2008) 304] and chemical erosion of porous graphite. To model the chemical erosion process due to thermal hydrogen ions, Kueppers cycle [J. Kueppers, Surf. Sci. Rep. 22 (1995) 249; M. Wittmann, J. Kueppers, J. Nucl. Mater. 227 (1996) 186] has been introduced. The model is applied to study hydrogen transport in deposits collected from the leading edge of neutralizers of Tore Supra. The effect of internal structure on chemical erosion is studied. The MD study [E. Salonen et al., J. Nucl. Mater. 290-293 (2001) 144] shows that the experimentally observed decrease of erosion yield at higher fluxes is due to the decrease of carbon collision cross-section at a surface due to shielding by hydrogen atom already present on the surface. Inspired by this study, a simple multi-scale model is developed to describe the flux dependence of chemical erosion. The idea is to use the local chemistry effect from the Kueppers model to calculate the hydrocarbon molecule formation process and then to find the release probability of the produced hydrocarbon based on the purely geometrical constraints. The model represents quite well the trends in experimental data.

  4. Rotational coherence spectroscopy at FLASH. Toward dynamic studies in nanosuperfluids

    Energy Technology Data Exchange (ETDEWEB)

    Kickermann, Andreas

    2013-07-15

    The field of molecular physics, which is focusing on molecular motion in the transition states of physical, chemical, and biological changes, is a wide-spread research area. It strives to reveal the structural and functional properties of molecules, the chemical bonds between atoms and the time evolution. Many processes occurring in nature upon electronic excitation proceed on the ultrafast femtosecond timescale and can be triggered by modern ultrashort femtosecond-laser sources under laboratory conditions. In the present thesis pump-probe studies were performed to follow molecular motion using ultrashort light pulses in the nanometer wavelength range provided by an XUV freeelectron laser (FEL). In detail, alignment of molecular species in space under field-free conditions was investigated. In the specific case of rotational wave packets in molecules the rotational dynamics shows characteristic temporal features, which contain a wealth of information on molecular structure and give insight into molecular coupling mechanisms, i.e. rotational constants and transition frequencies. Within this thesis, Rotational Coherence Spectroscopy (RCS) reveals wave-packet motion observed by subsequent Coulomb explosion of Raman excited carbon monoxide, which results in a time-dependent asymmetry of spatial fragmentation patterns. With the method presented here, the time resolution to elucidate the fast dynamics of strong couplings can be pushed toward a single rotational period even for the fastest rotors. This is due to large pump-probe delays with small subpicosecond step size. This kind of spectroscopy can also be expanded to molecular species, which are not accessible by other powerful spectroscopic methods, such as Fourier-transform microwave spectroscopy (FTMW). Furthermore, it allows to measure weak molecular couplings on a long timescale (large pump-probe delays), e.g. couplings of molecules in a solution or molecules dissolved in quantum fluids. This is valuable to

  5. Rotational coherence spectroscopy at FLASH. Toward dynamic studies in nanosuperfluids

    International Nuclear Information System (INIS)

    Kickermann, Andreas

    2013-07-01

    The field of molecular physics, which is focusing on molecular motion in the transition states of physical, chemical, and biological changes, is a wide-spread research area. It strives to reveal the structural and functional properties of molecules, the chemical bonds between atoms and the time evolution. Many processes occurring in nature upon electronic excitation proceed on the ultrafast femtosecond timescale and can be triggered by modern ultrashort femtosecond-laser sources under laboratory conditions. In the present thesis pump-probe studies were performed to follow molecular motion using ultrashort light pulses in the nanometer wavelength range provided by an XUV freeelectron laser (FEL). In detail, alignment of molecular species in space under field-free conditions was investigated. In the specific case of rotational wave packets in molecules the rotational dynamics shows characteristic temporal features, which contain a wealth of information on molecular structure and give insight into molecular coupling mechanisms, i.e. rotational constants and transition frequencies. Within this thesis, Rotational Coherence Spectroscopy (RCS) reveals wave-packet motion observed by subsequent Coulomb explosion of Raman excited carbon monoxide, which results in a time-dependent asymmetry of spatial fragmentation patterns. With the method presented here, the time resolution to elucidate the fast dynamics of strong couplings can be pushed toward a single rotational period even for the fastest rotors. This is due to large pump-probe delays with small subpicosecond step size. This kind of spectroscopy can also be expanded to molecular species, which are not accessible by other powerful spectroscopic methods, such as Fourier-transform microwave spectroscopy (FTMW). Furthermore, it allows to measure weak molecular couplings on a long timescale (large pump-probe delays), e.g. couplings of molecules in a solution or molecules dissolved in quantum fluids. This is valuable to

  6. Dynamics of Catalyst Nanoparticles

    DEFF Research Database (Denmark)

    Hansen, Thomas Willum; Cavalca, Filippo; Wagner, Jakob Birkedal

    and pharmaceuticals, and the cleanup of exhaust from automobiles and stationary power plants. Sintering, or thermal deactivation, is an important mechanism for the loss of catalyst activity. In order to initiate a systematic study of the dynamics and sintering of nanoparticles, various catalytic systems have been...... under gas exposure, dynamic phenomena such as sintering and growth can be observed with sub-Ångstrøm resolution. Metal nanoparticles contain the active sites in heterogeneous catalysts, which are important for many industrial applications including the production of clean fuels, chemicals...

  7. Chemical sciences, annual report 1993

    International Nuclear Information System (INIS)

    1994-10-01

    The Chemical Sciences Division (CSD) is one of eleven research Divisions of the Lawrence Berkeley Laboratory, a DOE National Laboratory. In FY 1993, the Division made considerable progress on developing two end-stations and a beamline to advance combustion dynamics at the Advanced Light Source (ALS). In support of DOE's national role in combustion research and chemical science, the beamline effort will enable researchers from around the world to make fundamental advances in understanding the structure and reactivity of critical reaction intermediates and transients, and in understanding the dynamics of elementary chemical reactions. The Division has continued to place a strong emphasis on full compliance with environmental health and safety guidelines and regulations and has made progress in technology transfer to industry. Finally, the Division has begun a new program in advanced battery research and development that should help strengthen industrial competitiveness both at home and abroad

  8. Chemical sciences, annual report 1993

    Energy Technology Data Exchange (ETDEWEB)

    1994-10-01

    The Chemical Sciences Division (CSD) is one of eleven research Divisions of the Lawrence Berkeley Laboratory, a DOE National Laboratory. In FY 1993, the Division made considerable progress on developing two end-stations and a beamline to advance combustion dynamics at the Advanced Light Source (ALS). In support of DOE`s national role in combustion research and chemical science, the beamline effort will enable researchers from around the world to make fundamental advances in understanding the structure and reactivity of critical reaction intermediates and transients, and in understanding the dynamics of elementary chemical reactions. The Division has continued to place a strong emphasis on full compliance with environmental health and safety guidelines and regulations and has made progress in technology transfer to industry. Finally, the Division has begun a new program in advanced battery research and development that should help strengthen industrial competitiveness both at home and abroad.

  9. Some concepts in condensed phase chemical kinetics

    International Nuclear Information System (INIS)

    Adelman, S.A.

    1986-01-01

    Some concepts in condensed phase chemical kinetics which have emerged from a recent rigorous statistical mechanical treatment of condensed phase chemical reaction dynamics (S.A. Adelman, Adv. Chem. Phys.53:61 (1983)) are discussed in simple physical terms

  10. Journal of Chemical Sciences | Indian Academy of Sciences

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences. B Jayachander Rao. Articles written in Journal of Chemical Sciences. Volume 119 Issue 5 September 2007 pp 401-407. Reactive chemical dynamics through conical intersections · S Ghosal B Jayachander Rao S Mahapatra · More Details Abstract Fulltext PDF. Reaction ...

  11. Bicanonical ab Initio Molecular Dynamics for Open Systems.

    Science.gov (United States)

    Frenzel, Johannes; Meyer, Bernd; Marx, Dominik

    2017-08-08

    Performing ab initio molecular dynamics simulations of open systems, where the chemical potential rather than the number of both nuclei and electrons is fixed, still is a challenge. Here, drawing on bicanonical sampling ideas introduced two decades ago by Swope and Andersen [ J. Chem. Phys. 1995 , 102 , 2851 - 2863 ] to calculate chemical potentials of liquids and solids, an ab initio simulation technique is devised, which introduces a fictitious dynamics of two superimposed but otherwise independent periodic systems including full electronic structure, such that either the chemical potential or the average fractional particle number of a specific chemical species can be kept constant. As proof of concept, we demonstrate that solvation free energies can be computed from these bicanonical ab initio simulations upon directly superimposing pure bulk water and the respective aqueous solution being the two limiting systems. The method is useful in many circumstances, for instance for studying heterogeneous catalytic processes taking place on surfaces where the chemical potential of reactants rather than their number is controlled and opens a pathway toward ab initio simulations at constant electrochemical potential.

  12. Isotope dependence of chemical erosion of carbon

    International Nuclear Information System (INIS)

    Reinhold, C.O.; Krstic, P.S.; Stuart, S.J.; Zhang, H.; Harris, P.R.; Meyer, F.W.

    2010-01-01

    We study the chemical erosion of hydrogen-supersaturated carbon due to bombardment by hydrogen isotopes H, D, and T at energies of 1-30 eV using classical molecular dynamics simulations. The chemical structure at the hydrogen-saturated interface (the distribution of terminal hydrocarbon moieties, in particular) shows a weak dependence on the mass of the impinging atoms. However, the sputtering yields increase considerably with increasing projectile mass. We analyze the threshold energies of chemical sputtering reaction channels and show that they are nearly mass independent, as expected from elementary bond-breaking chemical reactions involving hydrocarbons. Chemical sputtering yields for D impact are compared with new experimental data. Good agreement is found for small hydrocarbons but the simulations overestimate the production of large hydrocarbons for energies larger than 15 eV. We present a thorough analysis of the dependence of our simulations on the parameters of the bombardment schemes and discuss open questions and possible avenues for development.

  13. Co-Exposure with Fullerene May Strengthen Health Effects of Organic Industrial Chemicals

    DEFF Research Database (Denmark)

    Lehto, M.; Karilainen, T.; Rog, T.

    2014-01-01

    In vitro toxicological studies together with atomistic molecular dynamics simulations show that occupational co-exposure with C-60 fullerene may strengthen the health effects of organic industrial chemicals. The chemicals studied are acetophenone, benzaldehyde, benzyl alcohol, m-cresol, and toluene...... which can be used with fullerene as reagents or solvents in industrial processes. Potential co-exposure scenarios include a fullerene dust and organic chemical vapor, or a fullerene solution aerosolized in workplace air. Unfiltered and filtered mixtures of C-60 and organic chemicals represent different...... co-exposure scenarios in in vitro studies where acute cytotoxicity and immunotoxicity of C-60 and organic chemicals are tested together and alone by using human THP-1-derived macrophages. Statistically significant co-effects are observed for an unfiltered mixture of benzaldehyde and C-60 that is more...

  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. Dynamics in Complex Coacervates

    Science.gov (United States)

    Perry, Sarah

    Understanding the dynamics of a material provides detailed information about the self-assembly, structure, and intermolecular interactions present in a material. While rheological methods have long been used for the characterization of complex coacervate-based materials, it remains a challenge to predict the dynamics for a new system of materials. Furthermore, most work reports only qualitative trends exist as to how parameters such as charge stoichiometry, ionic strength, and polymer chain length impact self-assembly and material dynamics, and there is little information on the effects of polymer architecture or the organization of charges within a polymer. We seek to link thermodynamic studies of coacervation phase behavior with material dynamics through a carefully-controlled, systematic study of coacervate linear viscoelasticity for different polymer chemistries. We couple various methods of characterizing the dynamics of polymer-based complex coacervates, including the time-salt superposition methods developed first by Spruijt and coworkers to establish a more mechanistic strategy for comparing the material dynamics and linear viscoelasticity of different systems. Acknowledgment is made to the Donors of the American Chemical Society Petroleum Research Fund for support of this research.

  16. CHEMICAL PROPERTIES STUDYS OF PEATLANDON VARIOUS LANDUSE

    Directory of Open Access Journals (Sweden)

    Yondra Yondra

    2017-12-01

    Full Text Available Natural peat swamp forests converted can alter the soil chemical properties. This study aims to determine the extent to which changes in soil chemical properties that occur after the conversion of land from peat swamp forest to palm oil plantation, HTI Acacia crasicarpa, and sago plantation and to know which types of plants are sustainable on peatlands. The results showed that soil pH increased after the change of land function. While the water content decreased. Chemical properties such as C-organic, ash content, CEC, alkaline saturation, macro nutrients (NPK and bases can be changed also undergo changes after undergoing landuse changes, but no violations based on the law made by the government in pp No 25 of 2000 on the criteria of peatland damage and government regulation no. 150 of 2000 on the control of soil damage for biomass production. Sago is the most sustainable plant compared to others due to changes in soil chemical properties not too much different from other landuse although planted in the long term.

  17. An infrared free electron laser system for the proposed Chemical Dynamics Research Laboratory at LBL based on a 500 MHz superconducting linac

    International Nuclear Information System (INIS)

    Kim, K.J.; Byrns, R.; Chattopadhyay, S.; Donahue, R.; Edighoffer, J.; Gough, R.; Hoyer, E.; Leemans, W.; Staples, J.; Taylor, B.; Xie, M.

    1992-09-01

    We describe a new design of the Infrared Free Electron Laser (IRFEL) for the proposed Chemical Dynamics Research Laboratory (CDRL) at LBL. The design and choice of parameters are dictated by the unique requirements of the CDRL scientific program. The accelerator system is based on the 500 MHz superconducting cavity technology to achieve a wavelength stability of 10 -4

  18. Dynamic nuclear polarization of irradiated target materials

    International Nuclear Information System (INIS)

    Seely, M.L.

    1982-01-01

    Polarized nucleon targets used in high energy physics experiments usually employ the method of dynamic nuclear polarization (DNP) to polarize the protons or deuterons in an alcohol. DNP requires the presence of paramagnetic centers, which are customarily provided by a chemical dopant. These chemically doped targets have a relatively low polarizable nucleon content and suffer from loss of polarization when subjected to high doses of ionizing radiation. If the paramagnetic centers formed when the target is irradiated can be used in the DNP process, it becomes possible to produce targets using materials which have a relatively high polarizable nucleon content, but which are not easily doped by chemical means. Furthermore, the polarization of such targets may be much more radiation resistant. Dynamic nuclear polarization in ammonia, deuterated ammonia, ammonium hydroxide, methylamine, borane ammonia, butonal, ethane and lithium borohydride has been studied. These studies were conducted at the Stanford Linear Accelerator Center using the Yale-SLAC polarized target system. Results indicate that the use of ammonia and deuterated ammonia as polarized target materials would make significant increases in polarized target performance possible

  19. Journal of Chemical Sciences | Indian Academy of Sciences

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences. P K Chattaraj. Articles written in Journal of Chemical Sciences. Volume 115 Issue 3 June 2003 pp 195-218 Physical and Theoretical. Chemical reactivity of the compressed noble gas atoms and their reactivity dynamics during collisions with protons · P K Chattaraj B Maiti U ...

  20. Study of Intelligent Secure Chemical Inventory Management System

    Science.gov (United States)

    Shukran, Mohd Afizi Mohd; Naim Abdullah, Muhammad; Nazri Ismail, Mohd; Maskat, Kamaruzaman; Isa, Mohd Rizal Mohd; Shahfee Ishak, Muhammad; Adib Khairuddin, Muhamad

    2017-08-01

    Chemical inventory management system has been experiencing a new revolution from traditional inventory system which is manual to an automated inventory management system. In this paper, some review of the classic and modern approaches to chemical inventory management system has been discussed. This paper also describe about both type of inventory management. After a comparative analysis of the traditional method and automated method, it can be said that both methods have some distinctive characteristics. Moreover, the automated inventory management method has higher accuracy of calculation because the calculations are handled by software, eliminating possible errors and saving time. The automated inventory system also allows users and administrators to track the availability, location and consumption of chemicals. The study of this paper can provide forceful review analysis support for the chemical inventory management related research.

  1. Environmental high resolution electron microscopy and applications to chemical science

    OpenAIRE

    Boyes, Edward; Gai, Pratibha

    2017-01-01

    An environmental cell high resolution electron microscope (EHREM) has been developed for in situ studies of dynamic chemical reactions on the atomic scale. It allows access to metastable intermediate phases of catalysts and to sequences of reversible microstructural and chemical development associated with the activation, deactivation and poisoning of a catalyst. Materials transported through air can be restored or recreated and samples damaged, e.g. by dehydration, by the usual vacuum enviro...

  2. 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.

  3. Quantum indistinguishability in chemical reactions.

    Science.gov (United States)

    Fisher, Matthew P A; Radzihovsky, Leo

    2018-05-15

    Quantum indistinguishability plays a crucial role in many low-energy physical phenomena, from quantum fluids to molecular spectroscopy. It is, however, typically ignored in most high-temperature processes, particularly for ionic coordinates, implicitly assumed to be distinguishable, incoherent, and thus well approximated classically. We explore enzymatic chemical reactions involving small symmetric molecules and argue that in many situations a full quantum treatment of collective nuclear degrees of freedom is essential. Supported by several physical arguments, we conjecture a "quantum dynamical selection" (QDS) rule for small symmetric molecules that precludes chemical processes that involve direct transitions from orbitally nonsymmetric molecular states. As we propose and discuss, the implications of the QDS rule include ( i ) a differential chemical reactivity of para- and orthohydrogen, ( ii ) a mechanism for inducing intermolecular quantum entanglement of nuclear spins, ( iii ) a mass-independent isotope fractionation mechanism, ( iv ) an explanation of the enhanced chemical activity of "reactive oxygen species", ( v ) illuminating the importance of ortho-water molecules in modulating the quantum dynamics of liquid water, and ( vi ) providing the critical quantum-to-biochemical linkage in the nuclear spin model of the (putative) quantum brain, among others.

  4. Chemical Biodynamics Division. Annual report 1979

    Energy Technology Data Exchange (ETDEWEB)

    1980-08-01

    The Chemical Biodynamics Division of LBL continues to conduct basic research on the dynamics of living cells and on the interaction of radiant energy with organic matter. Many aspects of this basic research are related to problems of environmental and health effects of fossil fuel combustion, solar energy conversion and chemical/ viral carcinogenesis.

  5. Energy consumption of chemical uranium enrichment

    International Nuclear Information System (INIS)

    Miyake, T.; Takeda, K.; Obanawa, H.

    1987-01-01

    A quantitative study of chemical separation energy for enriching uranium-235 by the redox chromatography was conducted. Isotope exchange reactions between U 4+ -UO 2 2+ ions in the enrichment column are maintained by the redox reactions. The chemical separation energy is ultimately supplied by hydrogen and oxygen gas for regenerating redox agents. The redox energy for the isotope separation is theoretically predicted as a function of the dynamic enrichment factor observed in the chromatographic development of uranium adsorption band. Thermodynamic treatments of the equilibrium reactions implies and inverse redox reaction which can be enhanced by the chemical potential of the ion-exchange reaction of oxidant. Experimental results showed 30 to 90% recovery of the redox energy by the inverse reaction. These results will devise a simplified redox chromatography process where a number of columns in one module is reduced

  6. Ultrafast solvation dynamics explored by nonlinear optical spectroscopy

    NARCIS (Netherlands)

    Boeij, Wilhelmus Petrus de; Wiersma, D. A.

    1997-01-01

    Chemical reaction dynamics and chemical rate processes in the liquid phase are intimately connected to the specific interaction of the solvent on the reaction species. The strong coupling between the dissolved solute and the dynamical solvent causes fluctuations in the solute's energy levels. These

  7. Sensitivity analysis in molecular dynamics and chemical kinetics and a theory of intramolecular energy transfer in the presence of intense radiation fields

    International Nuclear Information System (INIS)

    Eslava, L.A.

    1983-01-01

    This thesis is an investigation of two topics in the area of molecular and chemical dynamics phenomena. The first topic, Sensitivity Analysis in Molecular Dynamics and Chemical Kinetics, explores the response of the numerical solutions to variation in the input information. After a brief consideration of elementary sensitivity coefficients (i.e. partial derivatives of observables with respect to model parameters), attention is focused on an entire new family of derived coefficients capable of exhibiting important aspects of the underlying dynamics. Each derived sensitivity coefficient has a unique physical interpretation in terms of an experiment or modeling calculation. Also, a fitting model for rotationally inelastic cross sections that accurately predicts cross sections away from the region of parameter space used in the fitting is presented. The global behavior of cross sections in parameter space is examined, and a nonlinear interpolation formula is suggested which utilizes sensitivity information. The second topic, A Theory of Intramolecular Energy Transfer in the Presence of Intense Radiation Fields, represents a theoretical formulation of energy redistribution based on stochastic considerations. The fundamental assumption is that a random phase approximation is valid at specific time intervals. This results in the replacement of the Schrodinger equation by a master-type equation, which is further approximated by a Fokker-Planck diffusion like equation. Energy transfer is described as a flow of probability among the quantum states, and the dissociation of dynamics are embodied in the boundary conditions. By virtue of the continuous character of the Fokker-Planck equation, the computational difficulty of its numerical solution depends only on the number of degrees of freedom and not on the number of states

  8. Urban Land: Study of Surface Run-off Composition and Its Dynamics

    Science.gov (United States)

    Palagin, E. D.; Gridneva, M. A.; Bykova, P. G.

    2017-11-01

    The qualitative composition of urban land surface run-off is liable to significant variations. To study surface run-off dynamics, to examine its behaviour and to discover reasons of these variations, it is relevant to use the mathematical apparatus technique of time series analysis. A seasonal decomposition procedure was applied to a temporary series of monthly dynamics with the annual frequency of seasonal variations in connection with a multiplicative model. The results of the quantitative chemical analysis of surface wastewater of the 22nd Partsjezd outlet in Samara for the period of 2004-2016 were used as basic data. As a result of the analysis, a seasonal pattern of variations in the composition of surface run-off in Samara was identified. Seasonal indices upon 15 waste-water quality indicators were defined. BOD (full), suspended materials, mineralization, chlorides, sulphates, ammonium-ion, nitrite-anion, nitrate-anion, phosphates (phosphorus), iron general, copper, zinc, aluminium, petroleum products, synthetic surfactants (anion-active). Based on the seasonal decomposition of the time series data, the contribution of trends, seasonal and accidental components of the variability of the surface run-off indicators was estimated.

  9. Do environmental dynamics matter in fate models? Exploring scenario dynamics for a terrestrial and an aquatic system.

    Science.gov (United States)

    Morselli, Melissa; Terzaghi, Elisa; Di Guardo, Antonio

    2018-01-24

    Nowadays, there is growing interest in inserting more ecological realism into risk assessment of chemicals. On the exposure evaluation side, this can be done by studying the complexity of exposure in the ecosystem, niche partitioning, e.g. variation of the exposure scenario. Current regulatory predictive approaches, to ensure simplicity and predictive ability, generally keep the scenario as static as possible. This could lead to under or overprediction of chemical exposure depending on the chemical and scenario simulated. To account for more realistic exposure conditions, varying temporally and spatially, additional scenario complexity should be included in currently used models to improve their predictive ability. This study presents two case studies (a terrestrial and an aquatic one) in which some polychlorinated biphenyls (PCBs) were simulated with the SoilPlusVeg and ChimERA models to show the importance of scenario variation in time (biotic and abiotic compartments). The results outlined the importance of accounting for planetary boundary layer variation and vegetation dynamics to accurately predict air concentration changes and the timing of chemical dispersion from the source in terrestrial systems. For the aquatic exercise, the results indicated the need to account for organic carbon forms (particulate and dissolved organic carbon) and vegetation biomass dynamics. In both cases the range of variation was up to two orders of magnitude depending on the congener and scenario, reinforcing the need for incorporating such knowledge into exposure assessment.

  10. Study of Dynamics of the Cross-linkinc Process of Hyperbranched Polymers

    Institute of Scientific and Technical Information of China (English)

    W.W.Sulkowski; S.MALanka; A.Sulkowska

    2007-01-01

    1 Results The description of the relaxation properties of polymers is the way to characterizate the influence of the polymer structure on its useful properties: stability and persistence. Synthesis and investigation of model compounds are needed to perform the physico-chemical characteristics of polymers. Instrumental methods as NMR and dielectric spectroscopy, thermogravimetric analysis and mechanical spectroscopy are used to this goal[1,2]. Dynamic mechanical thermal analysis (DMTA) is one of the most...

  11. Synchrotron radiation facilities for chemical applications

    International Nuclear Information System (INIS)

    Hatano, Yoshihiko

    1995-01-01

    Synchrotron radiation (SR) research is of great importance in understanding radiation chemistry, physics, and biology. It is also clearly recognized in the international chemical community that chemical applications of SR are greatly advanced and divided into 1) Molecular Spectroscopy and Dynamics Studies-Gases, Surfaces, and Condensed Matter- , 2) Radiation Chemistry and Photochemistry, 3) X-ray Structural and XAFS Studies-Crystals, Surfaces, and Liquids- , 4) Analytical Chemistry, and 5) Synthesis or R and D of New Materials. In this paper, a survey is given of recent advances in the application of SR to the chemistry of excitation and ionization of molecules, i.e., SR chemistry, in the wavelength region between near-ultraviolet and hard X-rays. The topics will be chosen from those obtained at some leading SR facilities. (J.P.N.)

  12. Amphibian Metamorphosis: A Sensitive Life Stage to Chemical and Non-chemical Stressors

    Science.gov (United States)

    Amphibian metamorphosis is a dynamic period of post-embryonic development which transforms the larval anuran into the juvenile. The body structure is remodeled through a variety of processes which may be perturbed by exposure to chemicals as well as other environmental stressors....

  13. Molecular dynamic and quantum chemical calculations for phthalazine derivatives as corrosion inhibitors of mild steel in 1 M HCl

    Energy Technology Data Exchange (ETDEWEB)

    Musa, Ahmed Y., E-mail: AMUSA6@UWO.CA [Department of Chemistry, University of Western Ontario, 1151 Richmond Street, London, Ontario, N6A 5B7 (Canada); Department of Chemical and Process Engineering, Universiti Kebangsaan Malaysia, Bangi, 43600 Selangor (Malaysia); Jalgham, Ramzi T.T.; Mohamad, Abu Bakar [Department of Chemical and Process Engineering, Universiti Kebangsaan Malaysia, Bangi, 43600 Selangor (Malaysia)

    2012-03-15

    Highlights: Black-Right-Pointing-Pointer The inhibition of three phthalazine derivatives was studied. Black-Right-Pointing-Pointer The inhibition efficiency increased in the following order: PTD < PT < PTO. Black-Right-Pointing-Pointer The adsorption energies were calculated using molecular dynamics simulations. Black-Right-Pointing-Pointer Quantum chemical parameters were calculated using the AM1, MNDO and PM3 methods. Black-Right-Pointing-Pointer The adsorption of phthalazine derivatives obeys the Langmuir adsorption isotherm. - Abstract: The abilities of phthalazine derivatives, including phthalazine (PT), phthalazone (PTO) and phthalhydrazide (PTD), to inhibit the corrosion of mild steel in 1 M HCl at 30 Degree-Sign C were studied using electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization measurements. Theoretical calculations were performed to investigate the electronic structures of the PT derivatives. Our results showed that the inhibition efficiencies of these derivatives improved with increases in concentration. The data also showed that PTD < PT < PTO in terms of the inhibiting efficiency. Theoretical calculations also revealed that PTO is expected to be the best inhibitor among the studied phthalazine derivatives.

  14. PHYSICO-CHEMICAL STUDIES OF DISAZO DYES DERIVED ...

    African Journals Online (AJOL)

    DJFLEX

    with disazo disperse dyes on synthetic polymer-fibres. (Venkataraman, 1974; Otutu et al., 2008). In this present study, the physico-chemical studies of disazo dyes derived from p-aminophenol recently prepared by our research group is described. We also described the kinetics of the dyes on nylon 6 fibre. In another study.

  15. Decay correction methods in dynamic PET studies

    International Nuclear Information System (INIS)

    Chen, K.; Reiman, E.; Lawson, M.

    1995-01-01

    In order to reconstruct positron emission tomography (PET) images in quantitative dynamic studies, the data must be corrected for radioactive decay. One of the two commonly used methods ignores physiological processes including blood flow that occur at the same time as radioactive decay; the other makes incorrect use of time-accumulated PET counts. In simulated dynamic PET studies using 11 C-acetate and 18 F-fluorodeoxyglucose (FDG), these methods are shown to result in biased estimates of the time-activity curve (TAC) and model parameters. New methods described in this article provide significantly improved parameter estimates in dynamic PET studies

  16. Spectroscopic analyses of chemical adaptation processes within microalgal biomass in response to changing environments

    Energy Technology Data Exchange (ETDEWEB)

    Vogt, Frank, E-mail: fvogt@utk.edu; White, Lauren

    2015-03-31

    Highlights: • Microalgae transform large quantities of inorganics into biomass. • Microalgae interact with their growing environment and adapt their chemical composition. • Sequestration capabilities are dependent on cells’ chemical environments. • We develop a chemometric hard-modeling to describe these chemical adaptation dynamics. • This methodology will enable studies of microalgal compound sequestration. - Abstract: Via photosynthesis, marine phytoplankton transforms large quantities of inorganic compounds into biomass. This has considerable environmental impacts as microalgae contribute for instance to counter-balancing anthropogenic releases of the greenhouse gas CO{sub 2}. On the other hand, high concentrations of nitrogen compounds in an ecosystem can lead to harmful algae blooms. In previous investigations it was found that the chemical composition of microalgal biomass is strongly dependent on the nutrient availability. Therefore, it is expected that algae’s sequestration capabilities and productivity are also determined by the cells’ chemical environments. For investigating this hypothesis, novel analytical methodologies are required which are capable of monitoring live cells exposed to chemically shifting environments followed by chemometric modeling of their chemical adaptation dynamics. FTIR-ATR experiments have been developed for acquiring spectroscopic time series of live Dunaliella parva cultures adapting to different nutrient situations. Comparing experimental data from acclimated cultures to those exposed to a chemically shifted nutrient situation reveals insights in which analyte groups participate in modifications of microalgal biomass and on what time scales. For a chemometric description of these processes, a data model has been deduced which explains the chemical adaptation dynamics explicitly rather than empirically. First results show that this approach is feasible and derives information about the chemical biomass

  17. Spectroscopic analyses of chemical adaptation processes within microalgal biomass in response to changing environments

    International Nuclear Information System (INIS)

    Vogt, Frank; White, Lauren

    2015-01-01

    Highlights: • Microalgae transform large quantities of inorganics into biomass. • Microalgae interact with their growing environment and adapt their chemical composition. • Sequestration capabilities are dependent on cells’ chemical environments. • We develop a chemometric hard-modeling to describe these chemical adaptation dynamics. • This methodology will enable studies of microalgal compound sequestration. - Abstract: Via photosynthesis, marine phytoplankton transforms large quantities of inorganic compounds into biomass. This has considerable environmental impacts as microalgae contribute for instance to counter-balancing anthropogenic releases of the greenhouse gas CO 2 . On the other hand, high concentrations of nitrogen compounds in an ecosystem can lead to harmful algae blooms. In previous investigations it was found that the chemical composition of microalgal biomass is strongly dependent on the nutrient availability. Therefore, it is expected that algae’s sequestration capabilities and productivity are also determined by the cells’ chemical environments. For investigating this hypothesis, novel analytical methodologies are required which are capable of monitoring live cells exposed to chemically shifting environments followed by chemometric modeling of their chemical adaptation dynamics. FTIR-ATR experiments have been developed for acquiring spectroscopic time series of live Dunaliella parva cultures adapting to different nutrient situations. Comparing experimental data from acclimated cultures to those exposed to a chemically shifted nutrient situation reveals insights in which analyte groups participate in modifications of microalgal biomass and on what time scales. For a chemometric description of these processes, a data model has been deduced which explains the chemical adaptation dynamics explicitly rather than empirically. First results show that this approach is feasible and derives information about the chemical biomass adaptations

  18. Chemical dynamics simulations of X- + CH3Y → XCH3 + Y- gas-phase S(N)2 nucleophilic substitution reactions. Nonstatistical dynamics and nontraditional reaction mechanisms.

    Science.gov (United States)

    Manikandan, Paranjothy; Zhang, Jiaxu; Hase, William L

    2012-03-29

    Extensive classical chemical dynamics simulations of gas-phase X(-) + CH(3)Y → XCH(3) + Y(-) S(N)2 nucleophilic substitution reactions are reviewed and discussed and compared with experimental measurements and predictions of theoretical models. The primary emphasis is on reactions for which X and Y are halogen atoms. Both reactions with the traditional potential energy surface (PES), which include pre- and postreaction potential energy minima and a central barrier, and reactions with nontraditional PESs are considered. These S(N)2 reactions exhibit important nonstatistical atomic-level dynamics. The X(-) + CH(3)Y → X(-)---CH(3)Y association rate constant is less than the capture model as a result of inefficient energy transfer from X(-)+ CH(3)Y relative translation to CH(3)Y rotation and vibration. There is weak coupling between the low-frequency intermolecular modes of the X(-)---CH(3)Y complex and higher frequency CH(3)Y intramolecular modes, resulting in non-RRKM kinetics for X(-)---CH(3)Y unimolecular decomposition. Recrossings of the [X--CH(3)--Y](-) central barrier is important. As a result of the above dynamics, the relative translational energy and temperature dependencies of the S(N)2 rate constants are not accurately given by statistical theory. The nonstatistical dynamics results in nonstatistical partitioning of the available energy to XCH(3) +Y(-) reaction products. Besides the indirect, complex forming atomic-level mechanism for the S(N)2 reaction, direct mechanisms promoted by X(-) + CH(3)Y relative translational or CH(3)Y vibrational excitation are possible, e.g., the roundabout mechanism.

  19. Dynamical studies of molecular systems. Progress report, February 1, 1980-October 27, 1980

    International Nuclear Information System (INIS)

    Rabitz, H.

    1980-01-01

    Research was carried out in the general areas of collision dynamics and chemical kinetics. Research on the following topics was pursued: computational kinetics and sensitivity analysis of hydrogen-oxygen combustion; chemical kinetic functional sensitivity analysis, elementary sensitivities; the selective preparation of excited vibrational states using the stimulated resonance raman effect; an exactly soluble many channel scattering model; further developments and applications of sensitivity analysis to collisional energy transfer; sensitivity analysis of rotational energy transfer processes to the intermolecular potential; a review of vibrational rotational collision processes; sensitivity analysis of differential cross sections to the intermolecular potential; and a non-local formulation of inelastic scattering as a basis for practical approximations

  20. Journal of Chemical Sciences | Indian Academy of Sciences

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences. CHINMAYEE CHOUDHURY. Articles written in Journal of Chemical Sciences. Volume 128 Issue 5 May 2016 pp 719-732 Regular Articles. Dynamic ligand-based pharmacophore modeling and virtual screening to identify mycobacterial cyclopropane synthase inhibitors.

  1. 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.

  2. Applications of the semiclassical spectral method to nuclear, atomic, molecular, and polymeric dynamics

    International Nuclear Information System (INIS)

    Koszykowski, M.L.; Pfeffer, G.A.; Noid, D.W.

    1987-01-01

    Nonlinear dynamics plays a dominant role in a variety of important problems in chemical physics. Examples are unimolecular reactions, infrared multiphoton decomposition of molecules, the pumping process of the gamma ray laser, dissociation of vibrationally excited state-selected van der Waals's complexes, and many other chemical and atomic processes. The present article discusses recent theoretical studies on the quasi-periodic and chaotic dynamic aspects of vibrational-rotational states of atomic, nuclear, and molecular systems using the semiclassical spectral method (SSM). The authors note that the coordinates, momenta, and so on, are found using classical mechanics in the studies included in this review. They outline the semiclassical spectral method and a wide variety of applications. Although this technique was first developed ten years ago, it has proved to be tremendously successful as a tool used in dynamics problems. Applications include problems in nonlinear dynamics, molecular and atomic spectra, surface science, astronomy and stellar dynamics, nuclear physics, and polymer physics

  3. Monitoring conformational dynamics with solid-state R1ρ experiments

    International Nuclear Information System (INIS)

    Quinn, Caitlin M.; McDermott, Ann E.

    2009-01-01

    A new application of solid-state rotating frame (R 1ρ ) relaxation experiments to observe conformational dynamics is presented. Studies on a model compound, dimethyl sulfone (DMS), show that R 1ρ relaxation due to reorientation of a chemical shift anisotropy (CSA) tensor undergoing chemical exchange can be used to monitor slow-to-intermediate timescale conformational exchange processes. Control experiments used d 6 -DMS and alanine to confirm that the technique is monitoring reorientation of the CSA tensor rather than dipolar interactions or methyl group rotation. The application of this method to proteins could represent a new site-specific probe of conformational dynamics

  4. Explosion of limit cycles and chaotic waves in a simple nonlinear chemical system

    DEFF Research Database (Denmark)

    Brøns, Morten; Sturis, Jeppe

    2001-01-01

    A model of an autocatalytic chemical reaction was employed to study the explosion of limit cycles and chaotic waves in a nonlinear chemical system. The bifurcation point was determined using asymptotic analysis and perturbations. Scaling laws for amplitude and period were derived. A strong sensit...... sensitivity was introduced due to bifurcation to infinity resulting in chaotic dynamics on adding diffusion....

  5. Understanding the physical and chemical changes on the three levels of the presentation of chemical concepts in students primary education

    OpenAIRE

    Bregar, Anja

    2017-01-01

    Physical and chemical changes are learning contents that address the essential chemical concepts in processes at particle level. When explaining chemical concepts at particle level, it is necessary to use various and appropriate visualization elements, such as (1) pictures, (2) photographs, (3) film excerpts (4) 2D or 3D stationary submicroscopic representations, (5) 2D and 3D dynamic contamination schemes, etc. This way, teachers can explain and interpret a chemical concept on three presenta...

  6. Kinetic studies of elementary chemical reactions

    Energy Technology Data Exchange (ETDEWEB)

    Durant, J.L. Jr. [Sandia National Laboratories, Livermore, CA (United States)

    1993-12-01

    This program concerning kinetic studies of elementary chemical reactions is presently focussed on understanding reactions of NH{sub x} species. To reach this goal, the author is pursuing experimental studies of reaction rate coefficients and product branching fractions as well as using electronic structure calculations to calculate transition state properties and reaction rate calculations to relate these properties to predicted kinetic behavior. The synergy existing between the experimental and theoretical studies allow one to gain a deeper insight into more complex elementary reactions.

  7. Study of the chemical sputtering in Tore-Supra

    International Nuclear Information System (INIS)

    Cambe, A.

    2002-01-01

    The work presented in this thesis focuses on the interactions between energetic particles coming from thermonuclear plasma and the inner components of a fusion machine. This interaction induces two major problems: erosion of the wall, and tritium retention. This report treats the erosion of carbon based materials. The first part is devoted to chemical sputtering, that appears to be the principal erosion mechanism, compared to physical sputtering and radiation enhanced sublimation that both can be limited. Chemical sputtering has been studied in situ in the tokamak Tore-Supra for ohmic and lower hybrid (LH) heated discharges, by means of mass spectrometry and optical spectroscopy. We have shown that it is necessary to take into account both methane and heavier hydrocarbons (C 2 D x and C 3 D y ) in the determination of the chemical sputtering yield. It is found that for the ohmic discharges, the sputtering yield of CD 4 (Y CD4 ) is highly flux (φ) dependent, showing a variation of the form: Y CD4 ∝ φ -0.23 . The experimental study also reveals that an increase of the surface temperature induces an augmentation of Y CD4 . The interpretation and the modelling of the experimental results have been performed with a Monte Carlo code (BBQ. In the second part of this work, we have developed and installed an infrared spectroscopy diagnostic in the 0.8-1.6, μm wavelength range dedicated to the measurement of surface temperature, and the identification of atomic and molecular lines emitted during plasma/wall interactions. In the third part, we present the feasibility study of an in situ tungsten deposition process at low temperature(<80 deg C) in order to suppress the chemical sputtering. This study shows that, with this method call Plasma Assisted Chemical Vapor Deposition (PACVD), we are able to coat the whole inner vessel of a tokamak with 1 μm of tungsten. (author)

  8. Effects of water scarcity and chemical pollution in aquatic ecosystems: State of the art.

    Science.gov (United States)

    Arenas-Sánchez, Alba; Rico, Andreu; Vighi, Marco

    2016-12-01

    Water scarcity is an expanding climate and human related condition, which drives and interacts with other stressors in freshwater ecosystems such as chemical pollution. In this study we provide an overview of the existing knowledge regarding the chemical fate, biological dynamics and the ecological risks of chemicals under water scarcity conditions. We evaluated a total of 15 studies dealing with the combined effects of chemicals and water scarcity under laboratory conditions and in the field. The results of these studies have been elaborated in order to evaluate additive, synergistic or antagonistic responses of the studied endpoints. As a general rule, it can be concluded that, in situations of water scarcity, the impacts of extreme water fluctuations are much more relevant than those of an additional chemical stressor. Nevertheless, the presence of chemical pollution may result in exacerbated ecological risks in some particular cases. We conclude that further investigations on this topic would take advantage on the focus on some specific issues. Experimental (laboratory and model ecosystem) studies should be performed on different biota groups and life stages (diapausing eggs, immature stages), with particular attention to those including traits relevant for the adaptation to water scarcity. More knowledge on species adaptations and recovery capacity is essential to predict community responses to multiple stressors and to assess the community vulnerability. Field studies should be performed at different scales, particularly in lotic systems, in order to integrate different functional dynamics of the river ecosystem. Combining field monitoring and experimental studies would be the best option to reach more conclusive, causal relationships on the effects of co-occurring stressors. Contribution of these studies to develop ecological models and scenarios is also suggested as an improvement for the prospective aquatic risk assessment of chemicals in (semi-)arid areas

  9. Seasonal dynamics of plankton communities coupled with ...

    African Journals Online (AJOL)

    In this study, we studied the influence of the physical-chemical and biological factors (bacterioplankton and phytoplankton abundances) for zooplankton dynamics in a Sidi Saâd reservoir in Centre of Tunisia. The samplings were carried out in spring, summer, autumn and winter (2005 to 2006) in the deepest station (surface ...

  10. Ion-Molecule Reaction Dynamics.

    Science.gov (United States)

    Meyer, Jennifer; Wester, Roland

    2017-05-05

    We review the recent advances in the investigation of the dynamics of ion-molecule reactions. During the past decade, the combination of single-collision experiments in crossed ion and neutral beams with the velocity map ion imaging detection technique has enabled a wealth of studies on ion-molecule reactions. These methods, in combination with chemical dynamics simulations, have uncovered new and unexpected reaction mechanisms, such as the roundabout mechanism and the subtle influence of the leaving group in anion-molecule nucleophilic substitution reactions. For this important class of reactions, as well as for many fundamental cation-molecule reactions, the information obtained with crossed-beam imaging is discussed. The first steps toward understanding micro-solvation of ion-molecule reaction dynamics are presented. We conclude with the presentation of several interesting directions for future research.

  11. Shape-dependent guidance of active Janus particles by chemically patterned surfaces

    Science.gov (United States)

    Uspal, W. E.; Popescu, M. N.; Tasinkevych, M.; Dietrich, S.

    2018-01-01

    Self-phoretic chemically active Janus particles move by inducing—via non-equilibrium chemical reactions occurring on their surfaces—changes in the chemical composition of the solution in which they are immersed. This process leads to gradients in chemical composition along the surface of the particle, as well as along any nearby boundaries, including solid walls. Chemical gradients along a wall can give rise to chemi-osmosis, i.e., the gradients drive surface flows which, in turn, drive flow in the volume of the solution. This bulk flow couples back to the particle, and thus contributes to its self-motility. Since chemi-osmosis strongly depends on the molecular interactions between the diffusing molecular species and the wall, the response flow induced and experienced by a particle encodes information about any chemical patterning of the wall. Here, we extend previous studies on self-phoresis of a sphere near a chemically patterned wall to the case of particles with rod-like, elongated shape. We focus our analysis on the new phenomenology potentially emerging from the coupling—which is inoperative for a spherical shape—of the elongated particle to the strain rate tensor of the chemi-osmotic flow. Via detailed numerical calculations, we show that the dynamics of a rod-like particle exhibits a novel ‘edge-following’ steady state: the particle translates along the edge of a chemical step at a steady distance from the step and with a steady orientation. Moreover, within a certain range of system parameters, the edge-following state co-exists with a ‘docking’ state (the particle stops at the step, oriented perpendicular to the step edge), i.e., a bistable dynamics occurs. These findings are rationalized as a consequence of the competition between the fluid vorticity and the rate of strain by using analytical theory based on the point-particle approximation which captures quasi-quantitatively the dynamics of the system.

  12. A mathematical basis for plant patterning derived from physico-chemical phenomena.

    Science.gov (United States)

    Beleyur, Thejasvi; Abdul Kareem, Valiya Kadavu; Shaji, Anil; Prasad, Kalika

    2013-04-01

    The position of leaves and flowers along the stem axis generates a specific pattern, known as phyllotaxis. A growing body of evidence emerging from recent computational modeling and experimental studies suggests that regulators controlling phyllotaxis are chemical, e.g. the plant growth hormone auxin and its dynamic accumulation pattern by polar auxin transport, and physical, e.g. mechanical properties of the cell. Here we present comprehensive views on how chemical and physical properties of cells regulate the pattern of leaf initiation. We further compare different computational modeling studies to understand their scope in reproducing the observed patterns. Despite a plethora of experimental studies on phyllotaxis, understanding of molecular mechanisms of pattern initiation in plants remains fragmentary. Live imaging of growth dynamics and physicochemical properties at the shoot apex of mutants displaying stable changes from one pattern to another should provide mechanistic insights into organ initiation patterns. Copyright © 2013 WILEY Periodicals, Inc.

  13. Interactive Dynamic-System Simulation

    CERN Document Server

    Korn, Granino A

    2010-01-01

    Showing you how to use personal computers for modeling and simulation, Interactive Dynamic-System Simulation, Second Edition provides a practical tutorial on interactive dynamic-system modeling and simulation. It discusses how to effectively simulate dynamical systems, such as aerospace vehicles, power plants, chemical processes, control systems, and physiological systems. Written by a pioneer in simulation, the book introduces dynamic-system models and explains how software for solving differential equations works. After demonstrating real simulation programs with simple examples, the author

  14. Molecular dynamics simulation studies of tailored nanostructured polymers

    Science.gov (United States)

    Liu, Lixin

    With recent advancements in the synthesis and characterization of polymeric materials, scientists are able to create multi-scale novel polymers with various cases of chemical functionalities, diversified topologies, as well as cross-linking networks. Due to those remarkable achievements, there are a broad range of possible applications of smart polymers in catalysis, in environmental remediation, and especially in drug-delivery. Because of rising interest in developing therapeutic drug binding to specific treating target, polymer chemists are in particular interests in design and engineering the drug delivery materials to be not only bio-compatible, but also to be capable of self-assembly at various in-vivo physiological stimulus. Both experimental and theoretical work indicate that the thermodynamic properties relating to the hydrophobic effect play an important role in determining self-assembly process. At the same time, computational simulation and modeling are powerful instruments to contribute to microscopic thermodynamics' understanding toward self-assembly phenomenon. Along with statistical approaches, constructing empirical model based on simulation results would also help predict for further development of tailored nano-structured materials. My Research mainly focused on investigating physical and chemical characteristics of polymer materials through molecular dynamics simulation and probing the fundamental thermodynamic driving force of self-assembly behavior. We tried to surmount technological obstacles in computational chemistry and build an efficient scheme to identify the physical and chemical Feature of molecules, to reproduce underlying properties, to understand the origin of thermodynamic signatures, and to speed up current trial and error process in screening new materials.

  15. Identification of critical chemical features for Aurora kinase-B inhibitors using Hip-Hop, virtual screening and molecular docking

    Science.gov (United States)

    Sakkiah, Sugunadevi; Thangapandian, Sundarapandian; John, Shalini; Lee, Keun Woo

    2011-01-01

    This study was performed to find the selective chemical features for Aurora kinase-B inhibitors using the potent methods like Hip-Hop, virtual screening, homology modeling, molecular dynamics and docking. The best hypothesis, Hypo1 was validated toward a wide range of test set containing the selective inhibitors of Aurora kinase-B. Homology modeling and molecular dynamics studies were carried out to perform the molecular docking studies. The best hypothesis Hypo1 was used as a 3D query to screen the chemical databases. The screened molecules from the databases were sorted based on ADME and drug like properties. The selective hit compounds were docked and the hydrogen bond interactions with the critical amino acids present in Aurora kinase-B were compared with the chemical features present in the Hypo1. Finally, we suggest that the chemical features present in the Hypo1 are vital for a molecule to inhibit the Aurora kinase-B activity.

  16. Computer processing of dynamic scintigraphic studies

    International Nuclear Information System (INIS)

    Ullmann, V.

    1985-01-01

    The methods are discussed of the computer processing of dynamic scintigraphic studies which were developed, studied or implemented by the authors within research task no. 30-02-03 in nuclear medicine within the five year plan 1981 to 85. This was mainly the method of computer processing radionuclide angiography, phase radioventriculography, regional lung ventilation, dynamic sequential scintigraphy of kidneys and radionuclide uroflowmetry. The problems are discussed of the automatic definition of fields of interest, the methodology of absolute volumes of the heart chamber in radionuclide cardiology, the design and uses are described of the multipurpose dynamic phantom of heart activity for radionuclide angiocardiography and ventriculography developed within the said research task. All methods are documented with many figures showing typical clinical (normal and pathological) and phantom measurements. (V.U.)

  17. Influence of chemical disorder on the electronic level spacing distribution of the Ag{sub 5083} nanoparticle: A tight-binding study

    Energy Technology Data Exchange (ETDEWEB)

    Medrano, L.R., E-mail: leonardoms20@gmail.com [Faculty of Physical Sciences, National University of San Marcos, P.O. Box 14-0149, Lima 14 (Peru); Landauro, C.V., E-mail: clandauros@unmsm.edu.pe [Faculty of Physical Sciences, National University of San Marcos, P.O. Box 14-0149, Lima 14 (Peru)

    2013-03-01

    In the present work we study, employing a tight-binding Hamiltonian, the influence of chemical disorder on the electronic level spacing distribution of a silver nanoparticle containing 5083 atoms (∼ 5.5 nm). This nanoparticle was obtained by molecular dynamics simulations with a tight-binding atomic potential. The results indicate that in the absence of disorder the level spacing distributions are similar to those expected for systems belonging to the Gaussian Orthogonal Ensemble. Whereas, after increasing the chemical disorder, the electronic level spacing distribution and the Σ{sub 2} statistics tend to the corresponding form for the Poisson Ensemble, i.e., the silver nanoparticle acquires an insulating character which is expected for strongly disordered systems. Hence, this kind of disorder produces the localization of the electronic states of the nanoparticle.

  18. Molecular dynamics simulations and quantum chemical calculations ...

    African Journals Online (AJOL)

    Molecular dynamic simulation results indicate that the imidazoline derivative molecules uses the imidazoline ring to effectively adsorb on the surface of iron, with the alkyl hydrophobic tail forming an n shape (canopy like covering) at geometry optimization and at 353 K. The n shape canopy like covering to a large extent may ...

  19. Journal of Chemical Sciences | Indian Academy of Sciences

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences. Biman Jana. Articles written in Journal of Chemical Sciences. Volume 119 Issue 5 September 2007 pp 343-350. Orientational dynamics and energy landscape features of thermotropic liquid crystals: An analogy with supercooled liquids · Biman Jana Biman Bagchi.

  20. Journal of Chemical Sciences | Indian Academy of Sciences

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences. Charusita Chakravarty. Articles written in Journal of Chemical Sciences. Volume 121 Issue 5 September 2009 pp 913-919. Evaluation of collective transport properties of ionic melts from molecular dynamics simulations · Manish Agarwal Charusita Chakravarty · More Details ...

  1. Effects of sample injection amount and time-of-flight mass spectrometric detection dynamic range on metabolome analysis by high-performance chemical isotope labeling LC-MS.

    Science.gov (United States)

    Zhou, Ruokun; Li, Liang

    2015-04-06

    The effect of sample injection amount on metabolome analysis in a chemical isotope labeling (CIL) liquid chromatography-mass spectrometry (LC-MS) platform was investigated. The performance of time-of-flight (TOF) mass spectrometers with and without a high-dynamic-range (HD) detection system was compared in the analysis of (12)C2/(13)C2-dansyl labeled human urine samples. An average of 1635 ± 21 (n = 3) peak pairs or putative metabolites was detected using the HD-TOF-MS, compared to 1429 ± 37 peak pairs from a conventional or non-HD TOF-MS. In both instruments, signal saturation was observed. However, in the HD-TOF-MS, signal saturation was mainly caused by the ionization process, while in the non-HD TOF-MS, it was caused by the detection process. To extend the MS detection range in the non-HD TOF-MS, an automated switching from using (12)C to (13)C-natural abundance peaks for peak ratio calculation when the (12)C peaks are saturated has been implemented in IsoMS, a software tool for processing CIL LC-MS data. This work illustrates that injecting an optimal sample amount is important to maximize the metabolome coverage while avoiding the sample carryover problem often associated with over-injection. A TOF mass spectrometer with an enhanced detection dynamic range can also significantly increase the number of peak pairs detected. In chemical isotope labeling (CIL) LC-MS, relative metabolite quantification is done by measuring the peak ratio of a (13)C2-/(12)C2-labeled peak pair for a given metabolite present in two comparative samples. The dynamic range of peak ratio measurement does not need to be very large, as only subtle changes of metabolite concentrations are encountered in most metabolomic studies where relative metabolome quantification of different groups of samples is performed. However, the absolute concentrations of different metabolites can be very different, requiring a technique to provide a wide detection dynamic range to allow the detection of as

  2. PIXE/RBS as a tool to study cementitious materials: Application to the dynamic leaching of concrete

    International Nuclear Information System (INIS)

    Llorente, I.; Castellote, M.; Gonzalez-Arrabal, R.; Ynsa, M.D.; Munoz-Martin, A.; Viedma, P.G. de; Castillo, A.; Martinez, I.; Andrade, C.; Zuloaga, P.; Ordonez, M.

    2009-01-01

    The suitability of the application of Ion Beam Analysis (IBA) techniques such as Particle Induced X-ray Emission spectrometry (PIXE) and Rutherford Backscattering Spectrometry (RBS) to elemental depth profiling in concrete is analysed, studying hardened samples of concrete prior to and after a dynamic leaching test. A calibration of the data has been done by comparing the results obtained by IBA techniques with those obtained by Chemical and Thermogravimetric Analysis (TG/DTA). From PIXE and RBS data relevant information about the migration of minor elements, within the concrete matrix after leaching is obtained.

  3. PIXE/RBS as a tool to study cementitious materials: Application to the dynamic leaching of concrete

    Energy Technology Data Exchange (ETDEWEB)

    Llorente, I., E-mail: irene@cenim.csic.e [Centro Nacional de Investigaciones Metalurgicas (CENIM-CSIC), Avda Gregorio del Amo, 8, 28040 Madrid (Spain); Castellote, M. [Instituto de Ciencias de la Construccion ' Eduardo Torroja' (IETcc-CSIC), Serrano Galvache, 4, 28033 Madrid (Spain); Gonzalez-Arrabal, R. [Parque Cientifico de Madrid, Campus de Cantoblanco, Einstein 13, 28049 Madrid (Spain); Ynsa, M.D.; Munoz-Martin, A. [Centro de Microanalisis de Materiales (CMAM), Universidad Autonoma de Madrid, Campus de Cantoblanco, 28049 Madrid (Spain); Viedma, P.G. de; Castillo, A.; Martinez, I.; Andrade, C. [Instituto de Ciencias de la Construccion ' Eduardo Torroja' (IETcc-CSIC), Serrano Galvache, 4, 28033 Madrid (Spain); Zuloaga, P.; Ordonez, M. [Empresa Nacional de Residuos Radiactivos, S.A. (ENRESA), Emilio Vargas, 7, 28043 Madrid (Spain)

    2009-12-15

    The suitability of the application of Ion Beam Analysis (IBA) techniques such as Particle Induced X-ray Emission spectrometry (PIXE) and Rutherford Backscattering Spectrometry (RBS) to elemental depth profiling in concrete is analysed, studying hardened samples of concrete prior to and after a dynamic leaching test. A calibration of the data has been done by comparing the results obtained by IBA techniques with those obtained by Chemical and Thermogravimetric Analysis (TG/DTA). From PIXE and RBS data relevant information about the migration of minor elements, within the concrete matrix after leaching is obtained.

  4. Study of interfacial phenomena for bio/chemical sensing applications

    Science.gov (United States)

    Min, Hwall

    This work presents the fundamental study of biological and chemical interfacial phenomena and (bio)chemical sensing applications using high frequency resonator arrays. To realize a versatile (bio)chemical sensing system for the fundamental study as well as their practical applications, the following three distinct components were studied and developed: i) detection platforms with high sensitivity, ii) novel innovative sensing materials with high selectivity, iii) analytical model for data interpretation. 8-pixel micromachined quartz crystal resonator (muQCR) arrays with a fundamental resonance frequency of 60 ¡V 90 MHz have been used to provide a reliable detection platform with high sensitivity. Room temperature ionic liquid (RTIL) has been explored and integrated into the sensing system as a smart chemical sensing material. The use of nanoporous gold (np-Au) enables the combination of the resonator and surface-enhanced Raman spectroscopy for both quantitative and qualitative measurement. A statistical model for the characterization of resonator behavior to study the protein adsorption kinetics is developed by random sequential adsorption (RSA) approach with the integration of an effective surface depletion theory. The investigation of the adsorption kinetics of blood proteins is reported as the fundamental study of biological phenomena using the proposed sensing system. The aim of this work is to study different aspects of protein adsorption and kinetics of adsorption process with blood proteins on different surfaces. We specifically focus on surface depletion effect in conjunction with the RSA model to explain the observed adsorption isotherm characteristics. A number of case studies on protein adsorption conducted using the proposed sensing system has been discussed. Effort is specifically made to understand adsorption kinetics, and the effect of surface on the adsorption process as well as the properties of the adsorbed protein layer. The second half of the

  5. An improved molecular dynamics algorithm to study thermodiffusion in binary hydrocarbon mixtures

    Science.gov (United States)

    Antoun, Sylvie; Saghir, M. Ziad; Srinivasan, Seshasai

    2018-03-01

    In multicomponent liquid mixtures, the diffusion flow of chemical species can be induced by temperature gradients, which leads to a separation of the constituent components. This cross effect between temperature and concentration is known as thermodiffusion or the Ludwig-Soret effect. The performance of boundary driven non-equilibrium molecular dynamics along with the enhanced heat exchange (eHEX) algorithm was studied by assessing the thermodiffusion process in n-pentane/n-decane (nC5-nC10) binary mixtures. The eHEX algorithm consists of an extended version of the HEX algorithm with an improved energy conservation property. In addition to this, the transferable potentials for phase equilibria-united atom force field were employed in all molecular dynamics (MD) simulations to precisely model the molecular interactions in the fluid. The Soret coefficients of the n-pentane/n-decane (nC5-nC10) mixture for three different compositions (at 300.15 K and 0.1 MPa) were calculated and compared with the experimental data and other MD results available in the literature. Results of our newly employed MD algorithm showed great agreement with experimental data and a better accuracy compared to other MD procedures.

  6. Evidence for Dynamic Chemical Kinetics at Individual Molecular Ruthenium Catalysts.

    Science.gov (United States)

    Easter, Quinn T; Blum, Suzanne A

    2018-02-05

    Catalytic cycles are typically depicted as possessing time-invariant steps with fixed rates. Yet the true behavior of individual catalysts with respect to time is unknown, hidden by the ensemble averaging inherent to bulk measurements. Evidence is presented for variable chemical kinetics at individual catalysts, with a focus on ring-opening metathesis polymerization catalyzed by the second-generation Grubbs' ruthenium catalyst. Fluorescence microscopy is used to probe the chemical kinetics of the reaction because the technique possesses sufficient sensitivity for the detection of single chemical reactions. Insertion reactions in submicron regions likely occur at groups of many (not single) catalysts, yet not so many that their unique kinetic behavior is ensemble averaged. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Human volunteer studies with non-pharmaceutical chemicals: metabolism and pharmacokinetic studies.

    Science.gov (United States)

    Wilks, M F; Woollen, B H

    1994-06-01

    1. Human volunteer studies are an essential part of drug development but their use in the area of non-pharmaceutical chemicals has so far been very limited. Such studies can have considerable value in the assessment and improvement of the safe use of chemicals. 2. Once metabolic pathways and target metabolites have been identified in volunteers this information can be used in studies in the workplace or in the general population. Studies should be performed selectively only if there is both a toxic hazard and a significant exposure potential. In addition, they should only be carried out if the required information cannot be obtained in any other way. 3. Volunteer studies with non-pharmaceuticals have become increasingly acceptable in the light of established international guidelines, no-fault compensation, improvements in study design and technical developments which allow the use of very low dose levels. The final decision on whether to carry out a study must always rest with an independent ethical committee. 4. The practical aspects of the study should be specified in a detailed protocol conforming with the principles of good clinical practice. The safety of volunteers must be of paramount concern throughout. Depending on the nature of the chemical and the study, it may be advisable to carry out studies in a clinical facility where equipment is available for the treatment of any emergencies that might occur. 5. Numerous investigators have now shown that human volunteer studies are ethically acceptable, practicable and yield important information. The risk to volunteers is minimal and this approach can lead to an improved foundation for occupational hygiene standards, more accurate risk assessment and thus better protection of the workforce and the general population.

  8. Chemical and radiation environmental risk management at the crossroads: Case studies

    International Nuclear Information System (INIS)

    Tran, N.; Burke, T.; Locke, P.

    1999-01-01

    Although many of the major environmental risk management decisions we face today require the simultaneous evaluation and control of both radiological and chemical risks, the separation of radiation and chemical risk management persists along legal, regulatory, programmatic, training and professional practice levels. In June 1998, a panel of 40 chemical and radiation risk experts met at an interactive workshop entitled 'Addressing the Similarities and Differences in Chemical and Radiation Environmental Risk Management,' in Annapolis, Maryland to discuss several perspectives on harmonizing chemical and radiation risk management approaches. At the conclusion of the meeting, workshop participants recommended that case studies of clean-up sites at which radioactive materials and hazardous chemical risks were addressed, be developed to help educate participants in the harmonization dialogue about their counterpart's issues, stimulate discussion and sharpen issues in a way that they can be resolved. Several key risk management issues that were highlighted from the discussion at the Annapolis meeting are being evaluated in the case studies. They include: decision criteria, costs and public/stakeholder input. This paper presents these key issues and the approach taken in the case studies. (author)

  9. Bioorthogonal Chemical Imaging for Biomedicine

    Science.gov (United States)

    Min, Wei

    2017-06-01

    Innovations in light microscopy have tremendously revolutionized the way researchers study biological systems with subcellular resolution. Although fluorescence microscopy is currently the method of choice for cellular imaging, it faces fundamental limitations for studying the vast number of small biomolecules. This is because relatively bulky fluorescent labels could introduce considerable perturbation to or even completely alter the native functions of vital small biomolecules. Hence, despite their immense functional importance, these small biomolecules remain largely undetectable by fluorescence microscopy. To address this challenge, we have developed a bioorthogonal chemical imaging platform. By coupling stimulated Raman scattering (SRS) microscopy, an emerging nonlinear Raman microscopy technique, with tiny and Raman-active vibrational probes (e.g., alkynes, nitriles and stable isotopes including 2H and 13C), bioorthogonal chemical imaging exhibits superb sensitivity, specificity, multiplicity and biocompatibility for imaging small biomolecules in live systems including tissues and organisms. Exciting biomedical applications such as imaging fatty acid metabolism related to lipotoxicity, glucose uptake and metabolism, drug trafficking, protein synthesis, DNA replication, protein degradation, RNA synthesis and tumor metabolism will be presented. This bioorthogonal chemical imaging platform is compatible with live-cell biology, thus allowing real-time imaging of small-molecule dynamics. Moreover, further chemical and spectroscopic strategies allow for multicolor bioorthogonal chemical imaging, a valuable technique in the era of "omics". We envision that the coupling of SRS microscopy with vibrational probes would do for small biomolecules what fluorescence microscopy of fluorophores has done for larger molecular species, bringing small molecules under the illumination of modern light microscopy.

  10. Contributions to the Study of Dynamic Absorbers, a Case Study

    Directory of Open Access Journals (Sweden)

    Monica Balcau

    2012-01-01

    Full Text Available Dynamic absorbers are used to reduce torsional vibrations. This paper studies the effect of a dynamic absorber attached to a mechanical system formed of three reduced masses which are acted on by one, two or three order x harmonics of a disruptive force.

  11. Different dynamic behaviors of the dissociation and recombination reactions in a model calculation of polyethylene by first-principles steered molecular dynamics simulation

    International Nuclear Information System (INIS)

    Higuchi, Yuji; Ishikawa, Takeshi; Ozawa, Nobuki; Chazeau, Laurent; Cavaillé, Jean-Yves; Kubo, Momoji

    2015-01-01

    Highlights: • We study the different dynamics of dissociation and recombination processes. • Hydrogen at the chain ends collides each other in the recombination process. • Dissociation and recombination processes take different pathway. - Abstract: We investigate the different dynamics of the stress-induced dissociation and recombination reactions in a model of polyethylene by a first-principles molecular dynamics simulation at the B3LYP/6-31g(d) level. The dissociation under external forces acting on the chemical reaction site at 300 K follows the same pathway as the one calculated by the static first-principles method because it has a similar activation barrier to that of the static first-principles calculation. On the other hand, in the recombination process, thermal fluctuations causes collisions between hydrogen atoms at the chain ends. Furthermore, when external forces do not directly act on the chemical reaction site, two different dissociation processes are observed. On the other hand, recombination process is not observed due to rarely contact of the radical carbon. These results indicate that dissociation and recombination dynamics are very different, showing the importance of the dynamic calculation.

  12. Structural studies on choline-carboxylate bio-ionic liquids by x-ray scattering and molecular dynamics.

    Science.gov (United States)

    Tanzi, Luana; Ramondo, Fabio; Caminiti, Ruggero; Campetella, Marco; Di Luca, Andrea; Gontrani, Lorenzo

    2015-09-21

    We report a X-ray diffraction and molecular dynamics study on three choline-based bio-ionic liquids, choline formate, [Ch] [For], choline propanoate, [Ch][Pro], and choline butanoate, [Ch][But]. For the first time, this class of ionic liquids has been investigated by X-ray diffraction. Experimental and theoretical structure factors have been compared for each term of the series. Local structural organization has been obtained from ab initio calculations through static models of isolated ion pairs and dynamic simulations of small portions of liquids through twelve, ten, and nine ion pairs for [Ch][For], [Ch][Pro], and [Ch][But], respectively. All the theoretical models indicate that cations and anions are connected by strong hydrogen bonding and form stable ion pairs in the liquid that are reminiscent of the static ab initio ion pairs. Different structural aspects may affect the radial distribution function, like the local structure of ion pairs and the conformation of choline. When small portions of liquids have been simulated by dynamic quantum chemical methods, some key structural features of the X-ray radial distribution function were well reproduced whereas the classical force fields here applied did not entirely reproduce all the observed structural features.

  13. Structural studies on choline-carboxylate bio-ionic liquids by x-ray scattering and molecular dynamics

    International Nuclear Information System (INIS)

    Tanzi, Luana; Ramondo, Fabio; Caminiti, Ruggero; Campetella, Marco; Di Luca, Andrea; Gontrani, Lorenzo

    2015-01-01

    We report a X-ray diffraction and molecular dynamics study on three choline-based bio-ionic liquids, choline formate, [Ch] [For], choline propanoate, [Ch][Pro], and choline butanoate, [Ch][But]. For the first time, this class of ionic liquids has been investigated by X-ray diffraction. Experimental and theoretical structure factors have been compared for each term of the series. Local structural organization has been obtained from ab initio calculations through static models of isolated ion pairs and dynamic simulations of small portions of liquids through twelve, ten, and nine ion pairs for [Ch][For], [Ch][Pro], and [Ch][But], respectively. All the theoretical models indicate that cations and anions are connected by strong hydrogen bonding and form stable ion pairs in the liquid that are reminiscent of the static ab initio ion pairs. Different structural aspects may affect the radial distribution function, like the local structure of ion pairs and the conformation of choline. When small portions of liquids have been simulated by dynamic quantum chemical methods, some key structural features of the X-ray radial distribution function were well reproduced whereas the classical force fields here applied did not entirely reproduce all the observed structural features

  14. Structural studies on choline-carboxylate bio-ionic liquids by x-ray scattering and molecular dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Tanzi, Luana; Ramondo, Fabio, E-mail: fabio.ramondo@univaq.it [Department of Physical and Chemical Sciences, University of L’Aquila, Via Vetoio, L’Aquila I-67100 (Italy); Caminiti, Ruggero; Campetella, Marco; Di Luca, Andrea; Gontrani, Lorenzo, E-mail: lorenzo.gontrani@uniroma1.it [Department of Chemistry, University of Rome ‘La Sapienza’, P.le Aldo Moro 5, I-00185 Rome (Italy)

    2015-09-21

    We report a X-ray diffraction and molecular dynamics study on three choline-based bio-ionic liquids, choline formate, [Ch] [For], choline propanoate, [Ch][Pro], and choline butanoate, [Ch][But]. For the first time, this class of ionic liquids has been investigated by X-ray diffraction. Experimental and theoretical structure factors have been compared for each term of the series. Local structural organization has been obtained from ab initio calculations through static models of isolated ion pairs and dynamic simulations of small portions of liquids through twelve, ten, and nine ion pairs for [Ch][For], [Ch][Pro], and [Ch][But], respectively. All the theoretical models indicate that cations and anions are connected by strong hydrogen bonding and form stable ion pairs in the liquid that are reminiscent of the static ab initio ion pairs. Different structural aspects may affect the radial distribution function, like the local structure of ion pairs and the conformation of choline. When small portions of liquids have been simulated by dynamic quantum chemical methods, some key structural features of the X-ray radial distribution function were well reproduced whereas the classical force fields here applied did not entirely reproduce all the observed structural features.

  15. Theoretical studies of combustion dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Bowman, J.M. [Emory Univ., Atlanta, GA (United States)

    1993-12-01

    The basic objectives of this research program are to develop and apply theoretical techniques to fundamental dynamical processes of importance in gas-phase combustion. There are two major areas currently supported by this grant. One is reactive scattering of diatom-diatom systems, and the other is the dynamics of complex formation and decay based on L{sup 2} methods. In all of these studies, the authors focus on systems that are of interest experimentally, and for which potential energy surfaces based, at least in part, on ab initio calculations are available.

  16. The PROSECCO server for chemical shift predictions in ordered and disordered proteins.

    Science.gov (United States)

    Sanz-Hernández, Máximo; De Simone, Alfonso

    2017-11-01

    The chemical shifts measured in solution-state and solid-state nuclear magnetic resonance (NMR) are powerful probes of the structure and dynamics of protein molecules. The exploitation of chemical shifts requires methods to correlate these data with the protein structures and sequences. We present here an approach to calculate accurate chemical shifts in both ordered and disordered proteins using exclusively the information contained in their sequences. Our sequence-based approach, protein sequences and chemical shift correlations (PROSECCO), achieves the accuracy of the most advanced structure-based methods in the characterization of chemical shifts of folded proteins and improves the state of the art in the study of disordered proteins. Our analyses revealed fundamental insights on the structural information carried by NMR chemical shifts of structured and unstructured protein states.

  17. Temperature dependent dynamics of DegP-trimer: A molecular dynamics study

    Directory of Open Access Journals (Sweden)

    Nivedita Rai

    2015-01-01

    Full Text Available DegP is a heat shock protein from high temperature requirement protease A family, which reacts to the environmental stress conditions in an ATP independent way. The objective of the present analysis emerged from the temperature dependent functional diversity of DegP between chaperonic and protease activities at temperatures below and above 28 °C, respectively. DegP is a multimeric protein and the minimal functional unit, DegP-trimer, is of great importance in understanding the DegP pathway. The structural aspects of DegP-trimer with respect to temperature variation have been studied using molecular dynamics simulations (for 100 ns and principal component analysis to highlight the temperature dependent dynamics facilitating its functional diversity. The DegP-trimer revealed a pronounced dynamics at both 280 and 320 K, when compared to the dynamics observed at 300 K. The LA loop is identified as the highly flexible region during dynamics and at extreme temperatures, the residues 46–80 of LA loop express a flip towards right (at 280 and left ( at 320 K with respect to the fixed β-sheet connecting the LA loop of protease for which Phe46 acts as one of the key residues. Such dynamics of LA loop facilitates inter-monomeric interaction with the PDZ1 domain of the neighbouring monomer and explains its active participation when DegP exists as trimer. Hence, the LA loop mediated dynamics of DegP-trimer is expected to provide further insight into the temperature dependent dynamics of DegP towards the understanding of its assembly and functional diversity in the presence of substrate.

  18. Role of protein dynamics in transmembrane receptor signalling

    DEFF Research Database (Denmark)

    Wang, Yong; Bugge, Katrine Østergaard; Kragelund, Birthe Brandt

    2018-01-01

    Cells are dependent on transmembrane receptors to communicate and transform chemical and physical signals into intracellular responses. Because receptors transport 'information', conformational changes and protein dynamics play a key mechanistic role. We here review examples where experiment...... to function. Because the receptors function in a heterogeneous environment and need to be able to switch between distinct functional states, they may be particularly sensitive to small perturbations that complicate studies linking dynamics to function....

  19. An integrated ion trap and time-of-flight mass spectrometer for chemical and photo- reaction dynamics studies

    International Nuclear Information System (INIS)

    Schowalter, Steven J.; Chen Kuang; Rellergert, Wade G.; Sullivan, Scott T.; Hudson, Eric R.

    2012-01-01

    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.

  20. Computational Fluid Dynamics Methods and Their Applications in Medical Science

    Directory of Open Access Journals (Sweden)

    Kowalewski Wojciech

    2016-12-01

    Full Text Available As defined by the National Institutes of Health: “Biomedical engineering integrates physical, chemical, mathematical, and computational sciences and engineering principles to study biology, medicine, behavior, and health”. Many issues in this area are closely related to fluid dynamics. This paper provides an overview of the basic concepts concerning Computational Fluid Dynamics and its applications in medicine.

  1. Study of the phenomena of crystallization of paraffin in the fluid-dynamic behavior of paraffinic crude - Phase 1

    International Nuclear Information System (INIS)

    Rodriguez, L; Castaneda, M

    2001-01-01

    The results obtained by relating the formation of wax crystals using traditional measurements such as cloud point, pour point and viscosity show the importance of analyzing the interactions among the chemical nature of crude oils, the physical-chemical variables and the fluid dynamics that cause different shapes and rates of crystallization. In addition, the specific value of viscosity should be measured at a certain temperature, as well as the rheological behavior of the crude oils during the process of formation and destruction of crystals due to shear rate. In order to carry out this study, a group of waxy crude oils was chosen. They were characterized considering the parameters mentioned above, and they were subjected to different cooling rates to microscopically observe the resulting morphologies, and to relate them to rheological behavior in a range of similar conditions that are obtained during hydrocarbon transport through pipelines. For this effect, laboratory tests were carried out, in addition to the scaling of results at the pilot plant level in a simulator to analyze the behavior of the fluids in dynamic or static conditions, in relation to prolonged pipeline downtime. This type of studies improves operational safety, offers considerable savings on additives, power, an increase in pumping capacity, and it also facilitates the selection of the most appropriate technology to control wax deposition

  2. Exact results in the large system size limit for the dynamics of the chemical master equation, a one dimensional chain of equations.

    Science.gov (United States)

    Martirosyan, A; Saakian, David B

    2011-08-01

    We apply the Hamilton-Jacobi equation (HJE) formalism to solve the dynamics of the chemical master equation (CME). We found exact analytical expressions (in large system-size limit) for the probability distribution, including explicit expression for the dynamics of variance of distribution. We also give the solution for some simple cases of the model with time-dependent rates. We derived the results of the Van Kampen method from the HJE approach using a special ansatz. Using the Van Kampen method, we give a system of ordinary differential equations (ODEs) to define the variance in a two-dimensional case. We performed numerics for the CME with stationary noise. We give analytical criteria for the disappearance of bistability in the case of stationary noise in one-dimensional CMEs.

  3. Microscopic study on dynamic barrier in fusion reactions

    International Nuclear Information System (INIS)

    Wu Xizhen; Tian Junlong; Zhao Kai; Li Zhuxia; Wang Ning

    2004-01-01

    The authors briefly review the fusion process of very heavy nuclear systems and some theoretical models. The authors propose a microscopic transport dynamic model, i.e. the Improved Quantum Molecular Dynamic model, for describing fusion reactions of heavy systems, in which the dynamical behavior of the fusion barrier in heavy fusion systems has been studied firstly. The authors find that with the incident energy decreasing the lowest dynamic barrier is obtained which approaches to the adiabatic static barrier and with increase of the incident energy the dynamic barrier goes up to the diabatic static barrier. The authors also indicate that how the dynamical fusion barrier is correlated with the development of the configuration of fusion partners along the fusion path. Associating the single-particle potentials obtained at different stages of fusion with the Two Center Shell Model, authors can study the time evolution of the single particle states of fusion system in configuration space of single particle orbits along the fusion path. (author)

  4. Current-driven dynamics in molecular-scale devices

    International Nuclear Information System (INIS)

    Seideman, Tamar

    2003-01-01

    We review recent theoretical work on current-triggered processes in molecular-scale devices - a field at the interface between solid state physics and chemical dynamics with potential applications in diverse areas, including artificial molecular machines, unimolecular transport, surface nanochemistry and nanolithography. The qualitative physics underlying current-triggered dynamics is first discussed and placed in context with several well-studied phenomena with which it shares aspects. A theory for modelling these dynamics is next formulated within a time-dependent scattering approach. Our end result provides useful insight into the system properties that determine the reaction outcome as well as a computationally convenient framework for numerical realization. The theory is applied to study single-molecule surface reactions induced by a scanning tunnelling microscope and current-triggered dynamics in single-molecule transistors. We close with a discussion of several potential applications of current-induced dynamics in molecular devices and several opportunities for future research. (topical review)

  5. A new methodology for studying nanoparticle interactions in biological systems: Dispersing titania in biocompatible media using chemical stabilisers

    Science.gov (United States)

    Ramirez-Garcia, Sonia; Chen, Lan; Morris, Michael A.; Dawson, Kenneth A.

    2011-11-01

    We report here a highly successful and original protocol for the dispersion of nanoparticles in biocompatible fluids for in vitro and in vivo studies of the nanoparticle-biology interaction. Titania is chosen as a suitable model as it is one of the priority materials listed by the OECD and small particles of the anatase structure are extensively used as e.g. photocatalysts in solar cells. Consequently, its delivery into the environment and its interaction with biological organisms is unavoidable. Therefore, its biological effect needs to be understood. In this work, we prepared stable nanoparticle dispersions of anatase aggregates using citrate stabilisations between 45 and 55 nm at concentrations of up to 10 mg mL-1. The optimum pH for this type of suspension was 7, resulting in ζ-potentials of approximately -50 mV. The stabilised aggregates were the subject of dialysis to produce stable dispersions without the chemical stabiliser, thus allowing studies in the absence of potentially toxic chemicals. Different sizing techniques such as Dynamic Light Scattering (DLS), Nanoparticle Tracking Analysis (NTA) and Differential Centrifuge Sedimentation (DCS) were used to characterise the different suspensions. The results obtained with each of these techniques are compared and a critical analysis of the suitability of each technique is given.We report here a highly successful and original protocol for the dispersion of nanoparticles in biocompatible fluids for in vitro and in vivo studies of the nanoparticle-biology interaction. Titania is chosen as a suitable model as it is one of the priority materials listed by the OECD and small particles of the anatase structure are extensively used as e.g. photocatalysts in solar cells. Consequently, its delivery into the environment and its interaction with biological organisms is unavoidable. Therefore, its biological effect needs to be understood. In this work, we prepared stable nanoparticle dispersions of anatase aggregates

  6. Study on Physical Properties and Chemical Composition of Some Myanmar Gems

    International Nuclear Information System (INIS)

    Kyaw Myint Htoo; Tun Khin; Sein Htoon

    2004-05-01

    Physical properties of some Myanmar gems were studied by using refractometer, dichroscope, polariscope, SG test, UV test and microscope. Then, chemical composition were investigated by XRF-technique. After that, gem identification, evaluation, colour improvement were studied according to these physical properties and chemical composition

  7. Toward prethreshold gate-based quantum simulation of chemical dynamics: using potential energy surfaces to simulate few-channel molecular collisions

    Science.gov (United States)

    Sornborger, Andrew T.; Stancil, Phillip; Geller, Michael R.

    2018-05-01

    One of the most promising applications of an error-corrected universal quantum computer is the efficient simulation of complex quantum systems such as large molecular systems. In this application, one is interested in both the electronic structure such as the ground state energy and dynamical properties such as the scattering cross section and chemical reaction rates. However, most theoretical work and experimental demonstrations have focused on the quantum computation of energies and energy surfaces. In this work, we attempt to make the prethreshold (not error-corrected) quantum simulation of dynamical properties practical as well. We show that the use of precomputed potential energy surfaces and couplings enables the gate-based simulation of few-channel but otherwise realistic molecular collisions. Our approach is based on the widely used Born-Oppenheimer approximation for the structure problem coupled with a semiclassical method for the dynamics. In the latter the electrons are treated quantum mechanically but the nuclei are classical, which restricts the collisions to high energy or temperature (typically above ≈ 10 eV). By using operator splitting techniques optimized for the resulting time-dependent Hamiltonian simulation problem, we give several physically realistic collision examples, with 3-8 channels and circuit depths < 1000.

  8. Progress report on SYVAC chemical speciation modelling studies during 1983/4

    International Nuclear Information System (INIS)

    Cross, J.; Smith, G.L.; Williams, D.R.

    1984-01-01

    This report summarises progress made on the SYVAC (System Variability Analysis program) chemical speciation project during 1983-4. Chemical speciation is defined and its importance in the SYVAC approach to Radioactive Waste Management is discussed. Computer modelling of chemical equilibria is described and the two programs presently operational at UWIST - SOLMNQ and MINEQL - are compared and discussed in detail. In view of the shortcomings of the databases supplied with these programs, a new database of equilibrium constants has been compiled containing 483 aqueous species and 329 solid phases, including data for the radionuclides uranium, plutonium, americium, neptunium and thorium. The collaborative work with AERE, Harwell, is reported. A leaching experiment carried out at Harwell has been modelled using the chemical speciation programs. The results for uranium, plutonium, americium and neptunium, are presented. However, the experimental data provided by AERE is insufficient for accurate simulations. Chemical speciation studies relating to specific sites require accurate characterisation of the groundwater, i.e. chemical composition, Eh and pH. In the absence of such information, preliminary studies have been made using an average granite groundwater. The results of these studies are presented and include solubility and speciation plots for uranium, plutonium, thorium and neptunium. The future aims of the project are discussed. (author)

  9. 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.

  10. 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

  11. Electro Thermal Chemical Gun Technology Study

    National Research Council Canada - National Science Library

    Diamond, P

    1999-01-01

    .... Michael Stroscio. Electro Thermal Chemical (ETC) gun technology refers to the use of plasma devices in place of traditional chemical ignitors to initiate the burning of high energy propellants in a controlled manner...

  12. RICE: a computer program for multicomponent chemically reactive flows at all speeds

    International Nuclear Information System (INIS)

    Rivard, W.C.; Farmer, O.A.; Butler, T.D.

    1974-11-01

    The fluid dynamics of chemically reactive mixtures are calculated at arbitrary flow speeds with the RICE program. The dynamics are governed by the two-dimensional, time-dependent Navier-Stokes equations together with the species transport equations and the mass-action rate equations for the chemical reactions. The mass and momentum equations for the mixture are solved implicitly by the ICE technique. The equations for total energy and species transport are solved explicitly while the chemical rate equations are solved implicitly with a time step that may be a submultiple of the hydrodynamic time step. Application is made to continuous wave HF chemical lasers to compute the supersonic mixing and chemical reactions that take place in the lasing cavity. (U.S.)

  13. Conformational fluctuation dynamics of domain I of human serum albumin in the course of chemically and thermally induced unfolding using fluorescence correlation spectroscopy.

    Science.gov (United States)

    Yadav, Rajeev; Sengupta, Bhaswati; Sen, Pratik

    2014-05-22

    The present study elucidates the involvement of conformational fluctuation dynamics during chemically and thermally induced unfolding of human serum albumin (HSA) by fluorescence correlation spectroscopic (FCS) study, time-resolved fluorescence measurements, and circular dichroism (CD) spectroscopic methods. Two fluorescent probes, tetramethylrhodamine-5-maleimide (TMR) and N-(7-dimethylamino-4-methylcoumarin-3-yl) iodoacetamide (DACIA) were used to selectively label the domain I of HSA through the reaction with cys-34 for these studies. The guanidine hydrochloride (GnHCl) induced global structural change of HSA is monitored through its hydrodynamic radius (r(H)) and CD response, which is found to be two step in nature. In FCS experiment, along with the diffusion time component we have observed an exponential relaxation time component (τ(R)) that has been ascribed to the concerted chain dynamics of HSA. Unlike in the global structural change, we found that the τ(R) value changes in a different manner in the course of the unfolding. The dependence of τ(R) on the concentration of GnHCl was best fitted with a four state model, indicating the involvement of two intermediate states during the unfolding process, which were not observed through the CD response and r(H) data. The fluorescence lifetime measurement also supports our observation of intermediate states during the unfolding of HSA. However, no such intermediate states were observed during thermally induced unfolding of HSA.

  14. Correlation study of chemical elements in phosphate ores

    International Nuclear Information System (INIS)

    Braganca, Maura Julia Camara da Silva

    1999-07-01

    Geological phenomena, 1) endogenous (volcanism, magmatic flow, metasomatism); 2) metamorphic (resultant of action of high temperature and pressure) and; 3) exogenous (intemperism, contamination) can modify the chemical composition of rocks soils. Thus, chemical elements with little mobility can be used as indicators of the previous geological situation before the occurrence of these phenomena and can sign the chemical composition of the initial formation. The elements with great mobility can already be used as indicators of the characteristic and intensity of the changes, can point out the influence factors and its space and time conditions. In this work the results of the study of phosphated samples ores coming from two alkaline-carbonatitic chimneys (Araxa and Catalao) and from a meta sedimentary rock (Patos de Minas), located phosphate rock deposit, are presented. The results were obtained using the instrumental neutron activation analysis, inductively coupled plasma-mass spectrometry (ICP-MS) and ICP-AES techniques. A comparison of the three types of samples ores, using chemical, crystallographic and statistical methods, shows that the Araxa and Catalao present some geochemical similarities and they are distinguished of Patos de Minas, despite its geographic proximity. (author)

  15. Molecular Dynamics Investigation of Efficient SO₂ Absorption by ...

    Indian Academy of Sciences (India)

    Ionic liquids are appropriate candidates for the absorption of acid gases such as SO₂. Six anion functionalized ionic liquids with different basicities have been studied for SO₂ absorption capacity by employing quantum chemical calculations and molecular dynamics (MD) simulations. Gas phase quantum calculations ...

  16. Structure and dynamics of the uranyl tricarbonate complex in aqueous solution: insights from quantum mechanical charge field molecular dynamics.

    Science.gov (United States)

    Tirler, Andreas O; Hofer, Thomas S

    2014-11-13

    This investigation presents the characterization of structural and dynamical properties of uranyl tricarbonate in aqueous solution employing an extended hybrid quantum mechanical/molecular mechanical (QM/MM) approach. It is shown that the inclusion of explicit solvent molecules in the quantum chemical treatment is essential to mimic the complex interaction occurring in an aqueous environment. Thus, in contrast to gas phase cluster calculations on a quantum chemical level proposing a 6-fold coordination of the three carbonates, the QMCF MD simulation proposes a 5-fold coordination. An extensive comparison of the simulation results to structural and dynamical data available in the literature was found to be in excellent agreement. Furthermore, this work is the first theoretical study on a quantum chemical level of theory able to observe the conversion of carbonate (CO₃²⁻) to bicarbonate (HCO₃⁻) in the equatorial coordination sphere of the uranyl ion. From a comparison of the free energy ΔG values for the unprotonated educt [UO₂(CO₃)₃]⁴⁻ and the protonated [UO₂(CO₃)₂(HCO₃)]³⁻, it could be concluded that the reaction equilibrium is strongly shifted toward the product state confirming the benignity for the observed protonation reaction. Structural properties and the three-dimensional arrangement of carbonate ligands were analyzed via pair-, three-body, and angular distributions, the dynamical properties were evaluated by hydrogen-bond correlation functions and vibrational power spectra.

  17. Molecular dynamics studies of superionic conductors

    International Nuclear Information System (INIS)

    Rahman, A.; Vashishta, P.

    1983-01-01

    Structural and dynamical properties of superionic conductors AgI and CuI are studied using molecular dynamics (MD) techniques. The model of these superionic conductors is based on the use of effective pair potentials. To determine the constants in these potentials, cohesive energy and bulk modulus are used as input: in addition one uses notions of ionic size based on the known crystal structure. Salient features of the MD technique are outlined. Methods of treating long range Coulomb forces are discussed in detail. This includes the manner of doing Ewald sum for MD cells of arbitrary shape. Features that can be incorporated to expedite the MD calculations are also discussed. A novel MD technique which allows for a dynamically controlled variation of the shape and size of the MD cell is described briefly. The development of this novel technique has made it possible to study structural phase transitions in superionic conductors. 68 references, 17 figures, 2 tables

  18. Perturbative study of the QCD phase diagram for heavy quarks at nonzero chemical potential: Two-loop corrections

    Science.gov (United States)

    Maelger, J.; Reinosa, U.; Serreau, J.

    2018-04-01

    We extend a previous investigation [U. Reinosa et al., Phys. Rev. D 92, 025021 (2015), 10.1103/PhysRevD.92.025021] of the QCD phase diagram with heavy quarks in the context of background field methods by including the two-loop corrections to the background field effective potential. The nonperturbative dynamics in the pure-gauge sector is modeled by a phenomenological gluon mass term in the Landau-DeWitt gauge-fixed action, which results in an improved perturbative expansion. We investigate the phase diagram at nonzero temperature and (real or imaginary) chemical potential. Two-loop corrections yield an improved agreement with lattice data as compared to the leading-order results. We also compare with the results of nonperturbative continuum approaches. We further study the equation of state as well as the thermodynamic stability of the system at two-loop order. Finally, using simple thermodynamic arguments, we show that the behavior of the Polyakov loops as functions of the chemical potential complies with their interpretation in terms of quark and antiquark free energies.

  19. Toxicity studies of drugs and chemicals in animals: An overview

    Directory of Open Access Journals (Sweden)

    S. Saganuwan

    2017-12-01

    Full Text Available Toxicity study is the investigation of either short or long-term toxic effects of a drug or chemical on animals. The toxicity is dose-dependent as asserted by Paracelsus over 500 years ago. However, short-term toxic effect is determined using median lethal dose (LD50 first introduced by Trevan in 1927 and revised many times. Presently there is a growing preponderance of rejection of scientific papers on acute toxicity study, simply because of the belief that in the current hazard and safety as-sessment of drugs and chemicals, LD50 values are no longer used. In view of this, literature search was carried out with a view to investigating the relevance of LD50 in development and assessment of drugs and chemicals. The findings revealed that in the past, many animals had been used for LD50 determination. OECD has reduced the number of test animals to 5–15 and presently it is further re-duced to 2–6. Acute toxicity study is being carried out in medicinal plants research and in the study of patent medicine. Although the application of LD50 has been drastically reduced, it is still applied and accepted in some parts of the world. Moreover, animals on which LD50 tests are conducted, should be allowed to die to see the end effect of the test drug or chemical because euthanisia of test animals may mask some toxicity signs of the test agents. Therefore, toxicity study of drugs and chemicals is a sci-entific process necessary for discovery and development of drugs as well as identification of potential toxicants.

  20. Spatially Localized Chemical Patterns around an A + B → Oscillator Front.

    Science.gov (United States)

    Budroni, M A; Lemaigre, L; Escala, D M; Muñuzuri, A P; De Wit, A

    2016-02-18

    When two gels, each loaded with a different set of reactants A and B of an oscillatory reaction, are brought into contact, reaction-diffusion patterns such as waves or Turing patterns can develop in the reactive contact zone. The initial condition which separates the reactants at the beginning leads to a localization in space of the different dynamical regimes accessible to the chemical oscillator. We study here both numerically and experimentally the composite traveling structures resulting from the interaction between chemical fronts and localized waves in the case in which the reactants of such an A + B → oscillator system are those of the canonical Belousov-Zhabotinsky (BZ) oscillating reaction. A transition between different dynamics is obtained by varying the initial concentration of the organic substrate of the BZ reactants, which is one of the parameters controlling the local excitability. We show that the dynamical regime (excitable or oscillatory) characterizing the BZ oscillator in the initial contact area is the key feature which determines the spatiotemporal evolution of the system. The experimental results are in qualitative agreement with the theoretical predictions.

  1. Molecular dynamics studies of the dynamics of supercooled Lennard-Jones liquids

    International Nuclear Information System (INIS)

    De Leeuw, S.W.; Brakkee, M.J.D.

    1990-01-01

    Results are presented of molecular dynamics experiments, in which the Lennard-Jones liquid is cooled isobarically into the metastable temperature region below the freezing temperature. The variation of the density-density and transverse current correlation functions with temperature is studied. We observed a power-law behaviour for the temperature dependence of dynamical properties (viscosity and coefficienty of self-diffusion) with an exponent in good agreement with prediction of mode coupling theories and recent experimental results. (author). 23 refs, 5 figs

  2. Dynamical Timescale of Pre-collapse Evolution Inferred from Chemical Distribution in the Taurus Molecular Cloud-1 (TMC-1) Filament

    Energy Technology Data Exchange (ETDEWEB)

    Choi, Yunhee; Lee, Jeong-Eun [School of Space Research, Kyung Hee University, 1732, Deogyeong-daero, Giheung-gu, Yongin-si, Gyeonggi-do 17104 (Korea, Republic of); Bourke, Tyler L. [Square Kilometre Array Organisation, Jodrell Bank Observatory, Lower Withington, Cheshire SK11 9DL (United Kingdom); II, Neal J. Evans, E-mail: yunhee.choi@khu.ac.kr, E-mail: jeongeun.lee@khu.ac.kr [Department of Astronomy, University of Texas at Austin, 2515 Speedway, Stop C1400, Austin, TX 78712-1205 (United States)

    2017-04-01

    We present observations and analyses of the low-mass star-forming region, Taurus Molecular Cloud-1 (TMC-1). CS ( J = 2–1)/N{sub 2}H{sup +} ( J = 1–0) and C{sup 17}O ( J = 2–1)/C{sup 18}O ( J = 2–1) were observed with the Five College Radio Astronomy Observatory and the Seoul Radio Astronomy Observatory, respectively. In addition, Spitzer infrared data and 1.2 mm continuum data observed with Max-Planck Millimetre Bolometer are used. We also perform chemical modeling to investigate the relative molecular distributions of the TMC-1 filament. Based on Spitzer observations, there is no young stellar object along the TMC-1 filament, while five Class II and one Class I young stellar objects are identified outside the filament. The comparison between column densities calculated from dust continuum and C{sup 17}O 2–1 line emission shows that CO is depleted much more significantly in the ammonia peak than in the cyanopolyyne peak, while the column densities calculated from the dust continuum are similar at the two peaks. N{sub 2}H{sup +} is not depleted much in either peak. According to our chemical calculation, the differential chemical distribution in the two peaks can be explained by different timescales required to reach the same density, i.e., by different dynamical processes.

  3. Exploring streamwater mixing dynamics via handheld thermal infrared imagery

    NARCIS (Netherlands)

    Antonelli, Marta; Klaus, Julian; Smettem, Keith; Teuling, Ryan; Pfister, Laurent

    2017-01-01

    Stream confluences are important hotspots of aquatic ecological processes. Water mixing dynamics at stream confluences influence physio-chemical characteristics of the stream as well as sediment mobilisation and pollutant dispersal. In this study, we investigated the potential for handheld

  4. Studies on modelling of bubble driven flows in chemical reactors

    Energy Technology Data Exchange (ETDEWEB)

    Grevskott, Sverre

    1997-12-31

    Multiphase reactors are widely used in the process industry, especially in the petrochemical industry. They very often are characterized by very good thermal control and high heat transfer coefficients against heating and cooling surfaces. This thesis first reviews recent advances in bubble column modelling, focusing on the fundamental flow equations, drag forces, transversal forces and added mass forces. The mathematical equations for the bubble column reactor are developed, using an Eulerian description for the continuous and dispersed phase in tensor notation. Conservation equations for mass, momentum, energy and chemical species are given, and the k-{epsilon} and Rice-Geary models for turbulence are described. The different algebraic solvers used in the model are described, as are relaxation procedures. Simulation results are presented and compared with experimental values. Attention is focused on the modelling of void fractions and gas velocities in the column. The energy conservation equation has been included in the bubble column model in order to model temperature distributions in a heated reactor. The conservation equation of chemical species has been included to simulate absorption of CO{sub 2}. Simulated axial and radial mass fraction profiles for CO{sub 2} in the gas phase are compared with measured values. Simulations of the dynamic behaviour of the column are also presented. 189 refs., 124 figs., 1 tab.

  5. Preliminary study of chemical compositional data from Amazon ceramics

    International Nuclear Information System (INIS)

    Toyota, Rosimeiri G.; Munita, Casimiro S.; Luz, Fabio A.; Neves, Eduardo G.; Oliveira, Paulo M.S.

    2005-01-01

    Eighty seven ceramic samples from Acutuba, Lago Grande and Osvaldo archaeological sites located in the confluence of the rivers Negro and Solimoes were submitted to chemical analysis using instrumental neutron activation analysis to determine As, Ba, Ce, Co, Cr, Cs, Eu, Fe, Hf, K, La, Lu, Rb, Na, Nd, Sb, Sc, Sm, Ta, Tb, Th, Yb, Zn, and U. The database were studied using the Mahalanobis distance, and discriminant analysis. The results showed that the ceramics of each site differ from each other in chemical composition and that they form three different groups. Chemical classification of the ceramics suggests that vessels were made locally, as only ceramics from the same area show homogeneity of data. (author)

  6. Inventory Control: A Small Electronic Device for Studying Chemical Kinetics.

    Science.gov (United States)

    Perez-Rodriguez, A. L.; Calvo-Aguilar, J. L.

    1984-01-01

    Shows how the rate of reaction can be studied using a simple electronic device that overcomes the difficulty students encounter in solving the differential equations describing chemical equilibrium. The device, used in conjunction with an oscilloscope, supplies the voltages that represent the chemical variables that take part in the equilibrium.…

  7. Quantum chemical studies of estrogenic compounds

    Science.gov (United States)

    Quantum chemical methods are potent tools to provide information on the chemical structure and electronic properties of organic molecules. Modern computational chemistry methods have provided a great deal of insight into the binding of estrogenic compounds to estrogenic receptors (ER), an important ...

  8. The dynamic behavior of the exohedral transition metal complexes ...

    Indian Academy of Sciences (India)

    NAIWRIT KARMODAK

    Special Issue on THEORETICAL CHEMISTRY/CHEMICAL DYNAMICS. The dynamic behavior ... The ab initio molecular dynamic simulations were performed at. 1200 K to ... boron clusters and the nature of polyhedral boranes suggested that ...

  9. Does the QCD vacuum build up a colour chemical potential dynamically?

    International Nuclear Information System (INIS)

    Sailer, K.; Greiner, W.

    1998-01-01

    The one-loop effective theory is found for QCD assuming an overcritical homogeneous gluon vector potential background that corresponds to a non-vanishing colour chemical potential. It is found that the vacuum is unstable against building up a non-vanishing colour chemical potential for sufficiently large number of flavours. (author)

  10. A Molecular Dynamics Study of Lunasin | Singh | South African ...

    African Journals Online (AJOL)

    A Molecular Dynamics Study of Lunasin. ... profile of lunasin,using classical molecular dynamics (MD) simulations at the time scale of 300 ns. ... Keywords: Lunasin, molecular dynamics, amber, CLASICO, α-helix, β-turn, PTRAJ, RGD, RMSD ...

  11. Dynamic transition in the structure of an energetic crystal during chemical reactions at shock front prior to detonation.

    Science.gov (United States)

    Nomura, Ken-Ichi; Kalia, Rajiv K; Nakano, Aiichiro; Vashishta, Priya; van Duin, Adri C T; Goddard, William A

    2007-10-05

    Mechanical stimuli in energetic materials initiate chemical reactions at shock fronts prior to detonation. Shock sensitivity measurements provide widely varying results, and quantum-mechanical calculations are unable to handle systems large enough to describe shock structure. Recent developments in reactive force-field molecular dynamics (ReaxFF-MD) combined with advances in parallel computing have paved the way to accurately simulate reaction pathways along with the structure of shock fronts. Our multimillion-atom ReaxFF-MD simulations of l,3,5-trinitro-l,3,5-triazine (RDX) reveal that detonation is preceded by a transition from a diffuse shock front with well-ordered molecular dipoles behind it to a disordered dipole distribution behind a sharp front.

  12. Diffusive Dynamics of Nanoparticles in Arrays of Nanoposts

    KAUST Repository

    He, Kai; Babaye Khorasani, Firoozeh; Retterer, Scott T.; Thomas, Darrell K.; Conrad, Jacinta C.; Krishnamoorti, Ramanan

    2013-01-01

    The diffusive dynamics of dilute dispersions of nanoparticles of diameter 200-400 nm were studied in microfabricated arrays of nanoposts using differential dynamic microscopy and single particle tracking. Posts of diameter 500 nm and height 10 μm were spaced by 1.2-10 μm on a square lattice. As the spacing between posts was decreased, the dynamics of the nanoparticles slowed. Moreover, the dynamics at all length scales were best represented by a stretched exponential rather than a simple exponential. Both the relative diffusivity and the stretching exponent decreased linearly with increased confinement and, equivalently, with decreased void volume. The slowing of the overall diffusive dynamics and the broadening distribution of nanoparticle displacements with increased confinement are consistent with the onset of dynamic heterogeneity and the approach to vitrification. © 2013 American Chemical Society.

  13. Diffusive Dynamics of Nanoparticles in Arrays of Nanoposts

    KAUST Repository

    He, Kai

    2013-06-25

    The diffusive dynamics of dilute dispersions of nanoparticles of diameter 200-400 nm were studied in microfabricated arrays of nanoposts using differential dynamic microscopy and single particle tracking. Posts of diameter 500 nm and height 10 μm were spaced by 1.2-10 μm on a square lattice. As the spacing between posts was decreased, the dynamics of the nanoparticles slowed. Moreover, the dynamics at all length scales were best represented by a stretched exponential rather than a simple exponential. Both the relative diffusivity and the stretching exponent decreased linearly with increased confinement and, equivalently, with decreased void volume. The slowing of the overall diffusive dynamics and the broadening distribution of nanoparticle displacements with increased confinement are consistent with the onset of dynamic heterogeneity and the approach to vitrification. © 2013 American Chemical Society.

  14. Moessbauer study of the chemical state of gold in gold ores

    International Nuclear Information System (INIS)

    Wagner, F.E.; Marion, P.H.; Regnard, J.-R.

    1986-01-01

    Information on the chemical state of gold in gold ores has been obtained by 197 Au Moessbauer spectroscopy in cases where the state of this element cannot be determined by such standard methods as optical or electron microscopy. Ore concentrates consisting mainly of pyrite or arsenopyrite and roasted ore and matte samples were studied. The results yielded directly the respective amounts of metallic and chemically bound gold. Unless the gold is metallic, its chemical state in the ores turns out to be different from that in the minerals studied so far as reference materials. The chemical processes taking place during various treatments of the ores, such as roasting or leaching, can also be followed by Moessbauer spectroscopy. It is hoped that Moessbauer spectroscopy will eventually facilitate the development of more efficient methods of gold extraction

  15. Paper spray mass spectrometry applied in the monitoring of a chemical system in dynamic chemical equilibrium: the redox process of methylene blue.

    Science.gov (United States)

    de Paula, Camila Cristina Almeida; Valadares, Alberto; Jurisch, Marina; Piccin, Evandro; Augusti, Rodinei

    2016-05-15

    The monitoring of chemical systems in dynamic equilibrium is not an easy task. This is due to the high rate at which the system returns to equilibrium after being perturbed, which hampers the possibility of following the aftereffects of the disturbance. In this context, it is necessary to use a fast analytical technique that requires no (or minimal) sample preparation, and which is capable of monitoring the species constituting the system in equilibrium. Paper spray ionization mass spectrometry (PS-MS), a recently introduced ambient ionization technique, has such characteristics and hence was chosen for monitoring a model system: the redox process of methylene blue. The model system evaluated herein was composed of three cationic species of methylene blue (MB), which coexist in a dynamic redox system: (1) [MB](+) of m/z 284 (cationic MB); (2) [MB + H + e](+•) of m/z 285 (the protonated form of a transient species resulting from the reduction of [MB](+) ); (3) [MB + 2H + 2e](+) or [leuco-MB + H](+) of m/z 286 (the protonated leuco form of MB). Aliquots of a MB solution were collected before and after the addition of a reducing agent (metallic zinc) and directly analyzed by PS-MS for identification of the predominant cationic species at different conditions. The mass spectra revealed that before the addition of the reducing agent the ion of m/z 284 (cationic MB) is the unique species. Upon the addition of the reducing agent and acid, however, the solution continuously undergo discoloration while reduced species derived directly from cationic MB (m/z 285 and 286) are detected in the mass spectra with increasing intensities. Fragmentation patterns obtained for each ionic species, i.e. [MB](+) , [MB + H + e](+•) and [leuco-MB + H](+) , shown to be consistent with the proposed structures. The PS-MS technique proved to be suitable for an in situ and 'near' real-time analysis of the dynamic equilibrium involving the redox of MB in aqueous medium. The data clearly

  16. Subseabed Disposal Project chemical response studies. Annual report, October 1982-September 1983

    International Nuclear Information System (INIS)

    Brush, L.H.

    1985-10-01

    Studies of the chemical response of deep-sea sediments to a subseabed repository for high-level radioactive waste continued during Fiscal Year 1983. Chemical Response Studies comprise Waste Package, Near-Field, and Far-Field Studies. This year, as in the past, investigators in the US Subseabed Disposal Project (SDP) carried out most of these chemical response experiments with red clay from the MPG 1 study location 1500 km north of Hawaii. The results of all studies carried out to date imply that oxidized red clay would form a highly effective barrier to radionuclides that form cationic species, but that anionic radionuclides would begin to escape from the sediment to the overlying water column on the order of thousands of years after emplacement. In Fiscal Year 1984, investigators in the US SDP will initiate chemical response studies with mildly reduced Atlantic clay- and carbonate-rich sediments in cooperation with the Sediment Barrier Task Group of the Organization for Economic Cooperation and Development - Nuclear Energy Agency Coordinated Program on the Assessment of the Subseabed Disposal of Radioactive Waste (Seabed Working Group). The objective of these US studies will be to quantify the chemical response of Atlantic sediments to a subseabed repository with a level of confidence similar to that for Pacific red clay

  17. Evolution of a chemically reacting plume in a ventilated room

    Science.gov (United States)

    Conroy, D. T.; Smith, Stefan G. Llewellyn; Caulfield, C. P.

    2005-08-01

    The dynamics of a second-order chemical reaction in an enclosed space driven by the mixing produced by a turbulent buoyant plume are studied theoretically, numerically and experimentally. An isolated turbulent buoyant plume source is located in an enclosure with a single external opening. Both the source and the opening are located at the bottom of the enclosure. The enclosure is filled with a fluid of a given density with a fixed initial concentration of a chemical. The source supplies a constant volume flux of fluid of different density containing a different chemical of known and constant concentration. These two chemicals undergo a second-order non-reversible reaction, leading to the creation of a third product chemical. For simplicity, we restrict attention to the situation where the reaction process does not affect the density of the fluids involved. Because of the natural constraint of volume conservation, fluid from the enclosure is continually vented. We study the evolution of the various chemical species as they are advected by the developing ventilated filling box process within the room that is driven by the plume dynamics. In particular, we study both the mean and vertical distributions of the chemical species as a function of time within the room. We compare the results of analogue laboratory experiments with theoretical predictions derived from reduced numerical models, and find excellent agreement. Important parameters for the behaviour of the system are associated with the source volume flux and specific momentum flux relative to the source specific buoyancy flux, the ratio of the initial concentrations of the reacting chemical input in the plume and the reacting chemical in the enclosed space, the reaction rate of the chemicals and the aspect ratio of the room. Although the behaviour of the system depends on all these parameters in a non-trivial way, in general the concentration within the room of the chemical input at the isolated source passes

  18. Comparing chemical reaction networks

    DEFF Research Database (Denmark)

    Cardelli, Luca; Tribastone, Mirco; Tschaikowski, Max

    2017-01-01

    We study chemical reaction networks (CRNs) as a kernel model of concurrency provided with semantics based on ordinary differential equations. We investigate the problem of comparing two CRNs, i.e., to decide whether the solutions of a source and of a target CRN can be matched for an appropriate...... choice of initial conditions. Using a categorical framework, we extend and unify model-comparison approaches based on dynamical (semantic) and structural (syntactic) properties of CRNs. Then, we provide an algorithm to compare CRNs, running linearly in time with respect to the cardinality of all possible...... comparisons. Finally, using a prototype implementation, CAGE, we apply our results to biological models from the literature....

  19. 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.

  20. Structures in dynamics finite dimensional deterministic studies

    CERN Document Server

    Broer, HW; van Strien, SJ; Takens, F

    1991-01-01

    The study of non-linear dynamical systems nowadays is an intricate mixture of analysis, geometry, algebra and measure theory and this book takes all aspects into account. Presenting the contents of its authors' graduate courses in non-linear dynamical systems, this volume aims at researchers who wish to be acquainted with the more theoretical and fundamental subjects in non-linear dynamics and is designed to link the popular literature with research papers and monographs. All of the subjects covered in this book are extensively dealt with and presented in a pedagogic

  1. Theory and application of quantum molecular dynamics

    CERN Document Server

    Zeng Hui Zhang, John

    1999-01-01

    This book provides a detailed presentation of modern quantum theories for treating the reaction dynamics of small molecular systems. Its main focus is on the recent development of successful quantum dynamics theories and computational methods for studying the molecular reactive scattering process, with specific applications given in detail for a number of benchmark chemical reaction systems in the gas phase and the gas surface. In contrast to traditional books on collision in physics focusing on abstract theory for nonreactive scattering, this book deals with both the development and the appli

  2. Chemical modification and blending of polymers in an extruder reactor

    International Nuclear Information System (INIS)

    Prut, Eduard V; Zelenetskii, Alexandr N

    2001-01-01

    Chemical modification and blending of polymers in an extruder reactor are discussed. Relationships between the parameters affecting the reaction kinetics, viz., mixing time, duration of a chemical reaction and the residence time of the system in the extruder reactor, and the structure of the materials produced are analysed. The mechanisms of (i) grafting of low-molecular-mass compounds onto polymers; (ii) reactions between terminal groups of different polymers and (iii) transesterification and interchange reactions are considered. The factors affecting the mechanism of dynamic vulcanisation and the properties of thermoplastic elastomers are identified. Solid-phase reactions of polysaccharides in an extruder are discussed. The priority aspects of studies on the chemical modification and blending of polymers are noted. The bibliography includes 90 references.

  3. 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.

  4. Chemistry of carbon in dynamic sodium

    Energy Technology Data Exchange (ETDEWEB)

    Lievens, F; Casteels, F [SCK/CEN, Mol (Belgium)

    1980-05-01

    The chemistry of carbon in sodium is described by its chemical activity measurements using alloy monitor foils, by its behaviour in the heat exchanger of the Na 2 sodium loop after 60,000 hours of operation, and by measurements with on-line meters. Efforts toward the identification of the carbon chemical states present in dynamic sodium, and responsible for the carbon chemical activity, are described. (author)

  5. Chemistry of carbon in dynamic sodium

    International Nuclear Information System (INIS)

    Lievens, F.; Casteels, F.

    1980-01-01

    The chemistry of carbon in sodium is described by its chemical activity measurements using alloy monitor foils, by its behaviour in the heat exchanger of the Na 2 sodium loop after 60,000 hours of operation, and by measurements with on-line meters. Efforts toward the identification of the carbon chemical states present in dynamic sodium, and responsible for the carbon chemical activity, are described. (author)

  6. An Analytical Study of Prostate-Specific Antigen Dynamics.

    Science.gov (United States)

    Esteban, Ernesto P; Deliz, Giovanni; Rivera-Rodriguez, Jaileen; Laureano, Stephanie M

    2016-01-01

    The purpose of this research is to carry out a quantitative study of prostate-specific antigen dynamics for patients with prostatic diseases, such as benign prostatic hyperplasia (BPH) and localized prostate cancer (LPC). The proposed PSA mathematical model was implemented using clinical data of 218 Japanese patients with histological proven BPH and 147 Japanese patients with LPC (stages T2a and T2b). For prostatic diseases (BPH and LPC) a nonlinear equation was obtained and solved in a close form to predict PSA progression with patients' age. The general solution describes PSA dynamics for patients with both diseases LPC and BPH. Particular solutions allow studying PSA dynamics for patients with BPH or LPC. Analytical solutions have been obtained and solved in a close form to develop nomograms for a better understanding of PSA dynamics in patients with BPH and LPC. This study may be useful to improve the diagnostic and prognosis of prostatic diseases.

  7. Dynamics of Chemical and Charge Transfer Reactions of Molecular Dications: IV. Proton Transfer and Reactions of Dication Isomers in the CHCl2+ +D2 System

    Czech Academy of Sciences Publication Activity Database

    Roithová, Jana; Žabka, Ján; Hrušák, Jan; Thissen, R.; Herman, Zdeněk

    2003-01-01

    Roč. 107, - (2003), s. 7347-7354 ISSN 1089-5639 R&D Projects: GA ČR GA203/00/0632; GA AV ČR KJB4040302 Grant - others:Barrande(FR) 2002-013-1 Institutional research plan: CEZ:AV0Z4040901 Keywords : dynamics of chemical * molecular dications * proton transfer Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.792, year: 2003

  8. Acoustic levitation of liquid drops: Dynamics, manipulation and phase transitions.

    Science.gov (United States)

    Zang, Duyang; Yu, Yinkai; Chen, Zhen; Li, Xiaoguang; Wu, Hongjing; Geng, Xingguo

    2017-05-01

    The technique of acoustic levitation normally produces a standing wave and the potential well of the sound field can be used to trap small objects. Since no solid surface is involved it has been widely applied for the study of fluid physics, nucleation, bio/chemical processes, and various forms of soft matter. In this article, we survey the works on drop dynamics in acoustic levitation, focus on how the dynamic behavior is related to the rheological properties and discuss the possibility to develop a novel rheometer based on this technique. We review the methods and applications of acoustic levitation for the manipulation of both liquid and solid samples and emphasize the important progress made in the study of phase transitions and bio-chemical analysis. We also highlight the possible open areas for future research. Copyright © 2017 Elsevier B.V. All rights reserved.

  9. 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.

  10. Molecular Dynamics Studies of Nanofluidic Devices

    DEFF Research Database (Denmark)

    Zambrano Rodriguez, Harvey Alexander

    of such devices. Computational nanofluidics complements experimental studies by providing detailed spatial and temporal information of the nanosystem. In this thesis, we conduct molecular dynamics simulations to study basic nanoscale devices. We focus our studies on the understanding of transport mechanism...... to drive fluids and solids at the nanoscale. Specifically, we present the results of three different research projects. Throughout the first part of this thesis, we include a comprenhensive introduction to computational nanofluidics and to molecular simulations, and describe the molecular dynamics...... in opposite direction to the imposed thermal gradient also we measure higher velocities as higher thermal gradients are imposed. Secondly, we present an atomistic analysis of a molecular linear motor fabricated of coaxial carbon nanotubes and powered by thermal gradients. The MD simulation results indicate...

  11. [Recent results in research on oscillatory chemical reactions].

    Science.gov (United States)

    Poros, Eszter; Kurin-Csörgei, Krisztina

    2014-01-01

    The mechanisms of the complicated periodical phenomenas in the nature (e.g. hearth beat, sleep cycle, circadian rhythms, etc) could be understood with using the laws of nonlinear chemical systems. In this article the newest result in the research of the subfield of nonlinear chemical dynamics aimed at constructing oscillatory chemical reactions, which are novel either in composition or in configuration, are presented. In the introductory part the concept of chemical periodicity is defined, then the forms as it can appear in time and space and the methods of their study are discussed. Detailed description of the experimental work that has resulted in two significant discoveries is provided. A method was developed to design pH-oscillators which are capable of operating under close conditions. The batch pH-oscillators are more convenient to use in some proposed applications than the equivalent CSTR variant. A redox oscillator that is new in composition was found. The permanganate oxidation of some amino acids was shown to take place according to oscillatory kinetics in a narrow range of the experimental parameters. The KMnO4 - glycine - Na2HPO4 system represents the first example in the family of manganese based oscillators where amino acids is involved. In the conclusion formal analogies between the simple chemical and some more complicated biological oscillatory phenomena are mentioned and the possibility of modeling periodic processes with the use of information gained from the studies of chemical oscillations is pointed out.

  12. A ring polymer molecular dynamics study of the isotopologues of the H + H2 reaction.

    Science.gov (United States)

    Suleimanov, Yury V; de Tudela, Ricardo Pérez; Jambrina, Pablo G; Castillo, Jesús F; Sáez-Rábanos, Vicente; Manolopoulos, David E; Aoiz, F Javier

    2013-03-14

    The inclusion of Quantum Mechanical (QM) effects such as zero point energy (ZPE) and tunneling in simulations of chemical reactions, especially in the case of light atom transfer, is an important problem in computational chemistry. In this respect, the hydrogen exchange reaction and its isotopic variants constitute an excellent benchmark for the assessment of approximate QM methods. In particular, the recently developed ring polymer molecular dynamics (RPMD) technique has been demonstrated to give very good results for bimolecular chemical reactions in the gas phase. In this work, we have performed a detailed RPMD study of the H + H(2) reaction and its isotopologues Mu + H(2), D + H(2) and Heμ + H(2), at temperatures ranging from 200 to 1000 K. Thermal rate coefficients and kinetic isotope effects have been computed and compared with exact QM calculations as well as with quasiclassical trajectories and experiment. The agreement with the QM results is good for the heaviest isotopologues, with errors ranging from 15% to 45%, and excellent for Mu + H(2), with errors below 15%. We have seen that RPMD is able to capture the ZPE effect very accurately, a desirable feature of any method based on molecular dynamics. We have also verified Richardson and Althorpe's prediction [J. O. Richardson and S. C. Althorpe, J. Chem. Phys., 2009, 131, 214106] that RPMD will overestimate thermal rates for asymmetric reactions and underestimate them for symmetric reactions in the deep tunneling regime. The ZPE effect along the reaction coordinate must be taken into account when assigning the reaction symmetry in the multidimensional case.

  13. Study of phenol extraction from coke-chemical sources

    Energy Technology Data Exchange (ETDEWEB)

    Catana, E.; Mateescu, I.; Giurcaneanu, V.; Bota, T.

    1990-09-01

    The paper presents an experimental study of the phase equilibrium in the coke-chemical tarphenols-solvent system (NaOH) solution and (phenolate solution) implied in the extraction of the phenols from coke-chemical sources. The possibility of using the phenolate solution as an extraction agent, thus making possible the improvement of the specific consumption and also simplifying the problem of the corrosion and of the waste water at the same time is presented. The influence of the solvent tar mass ratio on the selectivity of the process is discussed, this criterion being considered for establishing the conditions of the extraction. 2 figs., 7 tabs., 13 refs.

  14. Coupling dynamics and chemistry in the air pollution modelling of street canyons: A review.

    Science.gov (United States)

    Zhong, Jian; Cai, Xiao-Ming; Bloss, William James

    2016-07-01

    Air pollutants emitted from vehicles in street canyons may be reactive, undergoing mixing and chemical processing before escaping into the overlying atmosphere. The deterioration of air quality in street canyons occurs due to combined effects of proximate emission sources, dynamical processes (reduced dispersion) and chemical processes (evolution of reactive primary and formation of secondary pollutants). The coupling between dynamics and chemistry plays a major role in determining street canyon air quality, and numerical model approaches to represent this coupling are reviewed in this article. Dynamical processes can be represented by Computational Fluid Dynamics (CFD) techniques. The choice of CFD approach (mainly the Reynolds-Averaged Navier-Stokes (RANS) and Large-Eddy Simulation (LES) models) depends on the computational cost, the accuracy required and hence the application. Simplified parameterisations of the overall integrated effect of dynamics in street canyons provide capability to handle relatively complex chemistry in practical applications. Chemical processes are represented by a chemical mechanism, which describes mathematically the chemical removal and formation of primary and secondary species. Coupling between these aspects needs to accommodate transport, dispersion and chemical reactions for reactive pollutants, especially fast chemical reactions with time scales comparable to or shorter than those of typical turbulent eddies inside the street canyon. Different approaches to dynamical and chemical coupling have varying strengths, costs and levels of accuracy, which must be considered in their use for provision of reference information concerning urban canopy air pollution to stakeholders considering traffic and urban planning policies. Copyright © 2016 Elsevier Ltd. All rights reserved.

  15. Studying chemical reactions in biological systems with MBN Explorer

    DEFF Research Database (Denmark)

    Sushko, Gennady B.; Solov'yov, Ilia A.; Verkhovtsev, Alexey V.

    2016-01-01

    The concept of molecular mechanics force field has been widely accepted nowadays 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, we provide several illustrative case studies where dynamical topology is necessary. In particular, it is shown that the modified molecular mechanics force field can be applied...

  16. Using 1H and 13C NMR chemical shifts to determine cyclic peptide conformations: a combined molecular dynamics and quantum mechanics approach.

    Science.gov (United States)

    Nguyen, Q Nhu N; Schwochert, Joshua; Tantillo, Dean J; Lokey, R Scott

    2018-05-10

    Solving conformations of cyclic peptides can provide insight into structure-activity and structure-property relationships, which can help in the design of compounds with improved bioactivity and/or ADME characteristics. The most common approaches for determining the structures of cyclic peptides are based on NMR-derived distance restraints obtained from NOESY or ROESY cross-peak intensities, and 3J-based dihedral restraints using the Karplus relationship. Unfortunately, these observables are often too weak, sparse, or degenerate to provide unequivocal, high-confidence solution structures, prompting us to investigate an alternative approach that relies only on 1H and 13C chemical shifts as experimental observables. This method, which we call conformational analysis from NMR and density-functional prediction of low-energy ensembles (CANDLE), uses molecular dynamics (MD) simulations to generate conformer families and density functional theory (DFT) calculations to predict their 1H and 13C chemical shifts. Iterative conformer searches and DFT energy calculations on a cyclic peptide-peptoid hybrid yielded Boltzmann ensembles whose predicted chemical shifts matched the experimental values better than any single conformer. For these compounds, CANDLE outperformed the classic NOE- and 3J-coupling-based approach by disambiguating similar β-turn types and also enabled the structural elucidation of the minor conformer. Through the use of chemical shifts, in conjunction with DFT and MD calculations, CANDLE can help illuminate conformational ensembles of cyclic peptides in solution.

  17. 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

    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......, are challenging to assess with multiple chemical stressors impacting stream corridors. New approaches are urgently needed for identifying relevant sources, pathways and potential impacts for implementation of suitable source management and remedial measures. We developed a method for risk assessing chemical...... 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...

  18. Geochemical induced degradation of environmental chemicals

    Energy Technology Data Exchange (ETDEWEB)

    Parlar, H

    1984-09-01

    Attempts to correlate the concentration of organic chemicals in the environment with their production figures have resulted in a large deficit; this includes environmental chemicals such as chlorinated hydrocarbons. It has been assumed that analytical errors accounted for this deficit. Another explanation, however, allows for reactions of compounds under biotic and abiotic conditions. Because of the biostability of many organic chemicals biological transformation mechanisms can bring about slight change only. By contrast, abiotic environmental factors such as the UV-irradiation or decomposition on natural surfaces contribute considerably to the transformation of this substance class. An investigation of such abiotic charges of organic chemicals must therefore pay particular attention to dynamic and catalytic effects primarily attributable to the respective molecular state and interactions with the environment. This paper deals with the photoinduced reactions of organic substances adsorbed on natural surfaces and their significance for the degradability of environmental chemicals.

  19. On the Higher Moments of Particle Multiplicity, Chemical Freeze-Out, and QCD Critical Endpoint

    Directory of Open Access Journals (Sweden)

    A. Tawfik

    2013-01-01

    Full Text Available We calculate the first six nonnormalized moments of particle multiplicity within the framework of the hadron resonance gas model. In terms of the lower order moments and corresponding correlation functions, general expressions of higher order moments are derived. Thermal evolution of the first four normalized moments and their products (ratios are studied at different chemical potentials, so that it is possible to evaluate them at chemical freeze-out curve. It is found that a nonmonotonic behaviour reflecting the dynamical fluctuation and strong correlation of particles starts to appear from the normalized third order moment. We introduce novel conditions for describing the chemical freeze-out curve. Although the hadron resonance gas model does not contain any information on the criticality related to the chiral dynamics and singularity in the physical observables, we are able to find out the location of the QCD critical endpoint at μ ~ 350  MeV and temperature T ~ 162  MeV.

  20. Molecular dynamics study of the elastic response of crystalline, amorphous and chemically disordered NiZr2

    International Nuclear Information System (INIS)

    Willaime, F.; Rosato, V.

    1990-01-01

    We calculate the shear elastic constants of the alloy NiZr 2 by molecular dynamics simulations in the crystalline and amorphous phases as well as upon introduction of antisite defects in the crystal at T=300K. For S (long range order parameter) equal to 0.5, the system is amorphous and C' is larger than the same quantity relative to the crystal whereas C 44 and C 66 are smaller

  1. Single-Molecule Sensing with Nanopore Confinement: from Chemical Reactions to Biological Interactions.

    Science.gov (United States)

    Lin, Yao; Ying, Yi-Lun; Gao, Rui; Long, Yi-Tao

    2018-03-25

    The nanopore can generate an electrochemical confinement for single-molecule sensing which help understand the fundamental chemical principle in nanoscale dimensions. By observing the generated ionic current, individual bond-making and bond-breaking steps, single biomolecule dynamic conformational changes and electron transfer processes that occur within pore can be monitored with high temporal and current resolution. These single-molecule studies in nanopore confinement are revealing information about the fundamental chemical and biological processes that cannot be extracted from ensemble measurements. In this concept, we introduce and discuss the electrochemical confinement effects on single-molecule covalent reactions, conformational dynamics of individual molecules and host-guest interactions in protein nanopores. Then, we extend the concept of nanopore confinement effects to confine electrochemical redox reactions in solid-state nanopores for developing new sensing mechanisms. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Structure and dynamics of photosynthetic proteins studied by neutron scattering and molecular dynamic simulation

    International Nuclear Information System (INIS)

    Dellerue, Serge

    2000-01-01

    Understand the structure-dynamics-function relation in the case of proteins is essential. But few experimental techniques allow to have access to knowledge of fast internal movements of biological macromolecules. With the neutron scattering method, it has been possible to study the reorientation dynamics of side chains and of polypeptide skeleton for two proteins in terms of water or detergent and of temperature. With the use of the molecular dynamics method, essential for completing and interpreting the experimental data, it has been possible to assess the different contributions of the whole structure of proteins to the overall dynamics. It has been shown that the polypeptide skeleton presents an energy relaxation comparable to those of the side chains. Moreover, it has been explained that the protein dynamics can only be understood in terms of relaxation time distribution. (author) [fr

  3. Researchers study decontamination of chemical, biological warfare agents

    OpenAIRE

    Trulove, Susan

    2007-01-01

    The U.S. Army Research Office has awarded Virginia Tech a $680,000 grant over two years to build an instrument that can be used to study the chemistry of gases that will decompose both chemical and biological warfare agents on surfaces.

  4. A real-time Raman spectroscopy study of the dynamics of laser-thinning of MoS2 flakes to monolayers

    Science.gov (United States)

    Gu, Enyao; Wang, Qiyuan; Zhang, Youwei; Cong, Chunxiao; Hu, Laigui; Tian, Pengfei; Liu, Ran; Zhang, Shi-Li; Qiu, Zhi-Jun

    2017-12-01

    Transition metal dichalcogenides (TMDCs) in monolayer form have attracted a great deal of attention for electronic and optical applications. Compared to mechanical exfoliation and chemical synthesis, laser thinning is a novel and unique "on-demand" approach to fabricate monolayers or pattern desired shapes with high controllability and reproducibility. Its successful demonstration motivates a further exploration of the dynamic behaviour of this local thinning process. Here, we present an in-situ study of void formation by laser irradiation with the assistance of temporal Raman evolution. In the analysis of time-dependent Raman intensity, an empirical formula relating void size to laser power and exposure time is established. Void in thinner MoS2 flakes grows faster than in thicker ones as a result of reduced sublimation temperature in the two-dimensional (2D) materials. Our study provides useful insights into the laser-thinning dynamics of 2D TMDCs and guidelines for an effective control over the void formation.

  5. Application of dynamic Bayesian network to risk analysis of domino effects in chemical infrastructures

    International Nuclear Information System (INIS)

    Khakzad, Nima

    2015-01-01

    A domino effect is a low frequency high consequence chain of accidents where a primary accident (usually fire and explosion) in a unit triggers secondary accidents in adjacent units. High complexity and growing interdependencies of chemical infrastructures make them increasingly vulnerable to domino effects. Domino effects can be considered as time dependent processes. Thus, not only the identification of involved units but also their temporal entailment in the chain of accidents matter. More importantly, in the case of domino-induced fires which can generally last much longer compared to explosions, foreseeing the temporal evolution of domino effects and, in particular, predicting the most probable sequence of accidents (or involved units) in a domino effect can be of significance in the allocation of preventive and protective safety measures. Although many attempts have been made to identify the spatial evolution of domino effects, the temporal evolution of such accidents has been overlooked. We have proposed a methodology based on dynamic Bayesian network to model both the spatial and temporal evolutions of domino effects and also to quantify the most probable sequence of accidents in a potential domino effect. The application of the developed methodology has been demonstrated via a hypothetical fuel storage plant. - Highlights: • A Dynamic Bayesian Network methodology has been developed to model domino effects. • Considering time-dependencies, both spatial and temporal evolutions of domino effects have been modeled. • The concept of most probable sequence of accidents has been proposed instead of the most probable combination of accidents. • Using backward analysis, the most vulnerable units have been identified during a potential domino effect. • The proposed methodology does not need to identify a unique primary unit (accident) for domino effect modeling

  6. A Unification between Dynamical System Theory and Thermodynamics Involving an Energy, Mass, and Entropy State Space Formalism

    Directory of Open Access Journals (Sweden)

    Wassim M. Haddad

    2013-05-01

    Full Text Available In this paper, we combine the two universalisms of thermodynamics and dynamical systems theory to develop a dynamical system formalism for classical thermodynamics. Specifically, using a compartmental dynamical system energy flow model involving heat flow, work energy, and chemical reactions, we develop a state-space dynamical system model that captures the key aspects of thermodynamics, including its fundamental laws. In addition, we show that our thermodynamically consistent dynamical system model is globally semistable with system states converging to a state of temperature equipartition. Furthermore, in the presence of chemical reactions, we use the law of mass-action and the notion of chemical potential to show that the dynamic system states converge to a state of temperature equipartition and zero affinity corresponding to a state of chemical equilibrium.

  7. Beverton-Holt discrete pest management models with pulsed chemical control and evolution of pesticide resistance

    Science.gov (United States)

    Liang, Juhua; Tang, Sanyi; Cheke, Robert A.

    2016-07-01

    Pest resistance to pesticides is usually managed by switching between different types of pesticides. The optimal switching time, which depends on the dynamics of the pest population and on the evolution of the pesticide resistance, is critical. Here we address how the dynamic complexity of the pest population, the development of resistance and the spraying frequency of pulsed chemical control affect optimal switching strategies given different control aims. To do this, we developed novel discrete pest population growth models with both impulsive chemical control and the evolution of pesticide resistance. Strong and weak threshold conditions which guarantee the extinction of the pest population, based on the threshold values of the analytical formula for the optimal switching time, were derived. Further, we addressed switching strategies in the light of chosen economic injury levels. Moreover, the effects of the complex dynamical behaviour of the pest population on the pesticide switching times were also studied. The pesticide application period, the evolution of pesticide resistance and the dynamic complexity of the pest population may result in complex outbreak patterns, with consequent effects on the pesticide switching strategies.

  8. STRATAQ: A three-dimensional Chemical Transport Model of the stratosphere

    Directory of Open Access Journals (Sweden)

    B. Grassi

    2002-06-01

    Full Text Available A three-dimensional (3-D Chemical Transport Model (CTM of the stratosphere has been developed and used for a test study of the evolution of chemical species in the arctic lower stratosphere during winter 1996/97. This particular winter has been chosen for testing the model’s capabilities for its remarkable dynamical situation (very cold and strong polar vortex along with the availability of sparse chlorine, HNO3 and O3 data, showing also very low O3 values in late March/April. Due to those unusual features, the winter 1996/97 can be considered an excellent example of the impact of both dynamics and heterogeneous reactions on the chemistry of the stratosphere. Model integration has been performed from January to March 1997 and the resulting long-lived and short-lived tracer fields compared with available measurements. The model includes a detailed gas phase chemical scheme and a parameterization of the heterogeneous reactions occurring on liquid aerosol and polar stratospheric cloud (PSC surfaces. The transport is calculated using a semi-lagrangian flux scheme, forced by meteorological analyses. In such form, the STRATAQ CTM model is suitable for short-term integrations to study transport and chemical evolution related to "real" meteorological situations. Model simulation during the chosen winter shows intense PSC formation, with noticeable local HNO3 capture by PSCs, and the activation of vortex air leading to chlorine production and subsequent O3 destruction. The resulting model fields show generally good agreement with satellite data (MLS and TOMS, although the available observations, due to their limited number and time/space sparse nature, are not enough to effectively constraint the model. In particular, the model seems to perform well in reproducing the rapid processing of air inside the polar vortex on PSC converting reservoir species in active chlorine. In addition, it satisfactorily reproduces the morphology of the continuous O3

  9. STRATAQ: A three-dimensional Chemical Transport Model of the stratosphere

    Directory of Open Access Journals (Sweden)

    B. Grassi

    Full Text Available A three-dimensional (3-D Chemical Transport Model (CTM of the stratosphere has been developed and used for a test study of the evolution of chemical species in the arctic lower stratosphere during winter 1996/97. This particular winter has been chosen for testing the model’s capabilities for its remarkable dynamical situation (very cold and strong polar vortex along with the availability of sparse chlorine, HNO3 and O3 data, showing also very low O3 values in late March/April. Due to those unusual features, the winter 1996/97 can be considered an excellent example of the impact of both dynamics and heterogeneous reactions on the chemistry of the stratosphere. Model integration has been performed from January to March 1997 and the resulting long-lived and short-lived tracer fields compared with available measurements. The model includes a detailed gas phase chemical scheme and a parameterization of the heterogeneous reactions occurring on liquid aerosol and polar stratospheric cloud (PSC surfaces. The transport is calculated using a semi-lagrangian flux scheme, forced by meteorological analyses. In such form, the STRATAQ CTM model is suitable for short-term integrations to study transport and chemical evolution related to "real" meteorological situations. Model simulation during the chosen winter shows intense PSC formation, with noticeable local HNO3 capture by PSCs, and the activation of vortex air leading to chlorine production and subsequent O3 destruction. The resulting model fields show generally good agreement with satellite data (MLS and TOMS, although the available observations, due to their limited number and time/space sparse nature, are not enough to effectively constraint the model. In particular, the model seems to perform well in reproducing the rapid processing of air inside the polar vortex on PSC converting reservoir species in active chlorine. In addition, it

  10. The Use of Chemical-Chemical Interaction and Chemical Structure to Identify New Candidate Chemicals Related to Lung Cancer.

    Directory of Open Access Journals (Sweden)

    Lei Chen

    Full Text Available Lung cancer causes over one million deaths every year worldwide. However, prevention and treatment methods for this serious disease are limited. The identification of new chemicals related to lung cancer may aid in disease prevention and the design of more effective treatments. This study employed a weighted network, constructed using chemical-chemical interaction information, to identify new chemicals related to two types of lung cancer: non-small lung cancer and small-cell lung cancer. Then, a randomization test as well as chemical-chemical interaction and chemical structure information were utilized to make further selections. A final analysis of these new chemicals in the context of the current literature indicates that several chemicals are strongly linked to lung cancer.

  11. Hierarchical calibration and validation framework of bench-scale computational fluid dynamics simulations for solvent-based carbon capture. Part 2: Chemical absorption across a wetted wall column: Original Research Article: Hierarchical calibration and validation framework of bench-scale computational fluid dynamics simulations

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Chao [Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Physical and Computational Sciences Directorate; Xu, Zhijie [Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Physical and Computational Sciences Directorate; Lai, Kevin [Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Physical and Computational Sciences Directorate; Whyatt, Greg [Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Energy and Environment Directorate; Marcy, Peter W. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Sun, Xin [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Energy and Transportation Science Division

    2017-10-24

    Part 1 of this paper presents a numerical model for non-reactive physical mass transfer across a wetted wall column (WWC). In Part 2, we improved the existing computational fluid dynamics (CFD) model to simulate chemical absorption occurring in a WWC as a bench-scale study of solvent-based carbon dioxide (CO2) capture. In this study, to generate data for WWC model validation, CO2 mass transfer across a monoethanolamine (MEA) solvent was first measured on a WWC experimental apparatus. The numerical model developed in this work can account for both chemical absorption and desorption of CO2 in MEA. In addition, the overall mass transfer coefficient predicted using traditional/empirical correlations is conducted and compared with CFD prediction results for both steady and wavy falling films. A Bayesian statistical calibration algorithm is adopted to calibrate the reaction rate constants in chemical absorption/desorption of CO2 across a falling film of MEA. The posterior distributions of the two transport properties, i.e., Henry's constant and gas diffusivity in the non-reacting nitrous oxide (N2O)/MEA system obtained from Part 1 of this study, serves as priors for the calibration of CO2 reaction rate constants after using the N2O/CO2 analogy method. Finally, the calibrated model can be used to predict the CO2 mass transfer in a WWC for a wider range of operating conditions.

  12. 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)

  13. Ionic Liquids: Radiation Chemistry, Solvation Dynamics and Reactivity Patterns

    International Nuclear Information System (INIS)

    Wishart, J.F.

    2008-01-01

    Ionic liquids (ILs) are a rapidly expanding family of condensed-phase media with important applications in energy production, nuclear fuel and waste processing, improving the efficiency and safety of industrial chemical processes, and pollution prevention. ILs are generally nonvolatile, noncombustible, highly conductive, recyclable and capable of dissolving a wide variety of materials. They are finding new uses in chemical synthesis, catalysis, separations chemistry, electrochemistry and other areas. Ionic liquids have dramatically different properties compared to conventional molecular solvents, and they provide a new and unusual environment to test our theoretical understanding of charge transfer and other reactions. We are interested in how IL properties influence physical and dynamical processes that determine the stability and lifetimes of reactive intermediates and thereby affect the courses of chemical reactions and product distributions. Successful use of ionic liquids in radiation-filled environments, where their safety advantages could be significant, requires an understanding of ionic liquid radiation chemistry. For example, characterizing the primary steps of IL radiolysis will reveal radiolytic degradation pathways and suggest ways to prevent them or mitigate their effects on the properties of the material. An understanding of ionic liquid radiation chemistry will also facilitate pulse radiolysis studies of general chemical reactivity in ILs, which will aid in the development of applications listed above. Very early in our radiolysis studies it became evident that slow solvation dynamics of the excess electron in ILs (which vary over a wide viscosity range) increases the importance of pre-solvated electron reactivity and consequently alters product distributions. Parallel studies of IL solvation phenomena using coumarin-153 dynamic Stokes shifts and polarization anisotropy decay rates are done to compare with electron solvation studies and to evaluate

  14. IONIC LIQUIDS: RADIATION CHEMISTRY, SOLVATION DYNAMICS AND REACTIVITY PATTERNS

    International Nuclear Information System (INIS)

    WISHART, J.F.

    2007-01-01

    energy production, nuclear fuel and waste processing, improving the efficiency and safety of industrial chemical processes, and pollution prevention. ILs are generally nonvolatile, noncombustible, highly conductive, recyclable and capable of dissolving a wide variety of materials. They are finding new uses in chemical synthesis, catalysis, separations chemistry, electrochemistry and other areas. Ionic liquids have dramatically different properties compared to conventional molecular solvents, and they provide a new and unusual environment to test our theoretical understanding of charge transfer and other reactions. We are interested in how IL properties influence physical and dynamical processes that determine the stability and lifetimes of reactive intermediates and thereby affect the courses of chemical reactions and product distributions. Successful use of ionic liquids in radiation-filled environments, where their safety advantages could be significant, requires an understanding of ionic liquid radiation chemistry. For example, characterizing the primary steps of IL radiolysis will reveal radiolytic degradation pathways and suggest ways to prevent them or mitigate their effects on the properties of the material. An understanding of ionic liquid radiation chemistry will also facilitate pulse radiolysis studies of general chemical reactivity in ILs, which will aid in the development of applications listed above. Very early in our radiolysis studies it became evident that slow solvation dynamics of the excess electron in ILs (which vary over a wide viscosity range) increases the importance of pre-solvated electron reactivity and consequently alters product distributions. Parallel studies of IL solvation phenomena using coumarin-153 dynamic Stokes shifts and polarization anisotropy decay rates are done to compare with electron solvation studies and to evaluate the influence of ILs on charge transport processes. Methods. Picosecond pulse radiolysis studies at BNL

  15. Hierarchical calibration and validation framework of bench-scale computational fluid dynamics simulations for solvent-based carbon capture. Part 2: Chemical absorption across a wetted wall column: Original Research Article: Hierarchical calibration and validation framework of bench-scale computational fluid dynamics simulations

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Chao [Pacific Northwest National Laboratory, Physical and Computational Sciences Directorate, Richland WA; Xu, Zhijie [Pacific Northwest National Laboratory, Physical and Computational Sciences Directorate, Richland WA; Lai, Kevin [Pacific Northwest National Laboratory, Physical and Computational Sciences Directorate, Richland WA; Whyatt, Greg [Energy and Environment Directorate, Pacific Northwest National Laboratory, Richland WA; Marcy, Peter W. [Los Alamos National Laboratory, Statistical Sciences Group, Los Alamos NM; Sun, Xin [Oak Ridge National Laboratory, Energy and Transportation Science Division, Oak Ridge TN

    2017-10-24

    The first part of this paper (Part 1) presents a numerical model for non-reactive physical mass transfer across a wetted wall column (WWC). In Part 2, we improved the existing computational fluid dynamics (CFD) model to simulate chemical absorption occurring in a WWC as a bench-scale study of solvent-based carbon dioxide (CO2) capture. To generate data for WWC model validation, CO2 mass transfer across a monoethanolamine (MEA) solvent was first measured on a WWC experimental apparatus. The numerical model developed in this work has the ability to account for both chemical absorption and desorption of CO2 in MEA. In addition, the overall mass transfer coefficient predicted using traditional/empirical correlations is conducted and compared with CFD prediction results for both steady and wavy falling films. A Bayesian statistical calibration algorithm is adopted to calibrate the reaction rate constants in chemical absorption/desorption of CO2 across a falling film of MEA. The posterior distributions of the two transport properties, i.e., Henry’s constant and gas diffusivity in the non-reacting nitrous oxide (N2O)/MEA system obtained from Part 1 of this study, serves as priors for the calibration of CO2 reaction rate constants after using the N2O/CO2 analogy method. The calibrated model can be used to predict the CO2 mass transfer in a WWC for a wider range of operating conditions.

  16. Time-resolved resonance fluorescence spectroscopy for study of chemical reactions in laser-induced plasmas.

    Science.gov (United States)

    Liu, Lei; Deng, Leimin; Fan, Lisha; Huang, Xi; Lu, Yao; Shen, Xiaokang; Jiang, Lan; Silvain, Jean-François; Lu, Yongfeng

    2017-10-30

    Identification of chemical intermediates and study of chemical reaction pathways and mechanisms in laser-induced plasmas are important for laser-ablated applications. Laser-induced breakdown spectroscopy (LIBS), as a promising spectroscopic technique, is efficient for elemental analyses but can only provide limited information about chemical products in laser-induced plasmas. In this work, time-resolved resonance fluorescence spectroscopy was studied as a promising tool for the study of chemical reactions in laser-induced plasmas. Resonance fluorescence excitation of diatomic aluminum monoxide (AlO) and triatomic dialuminum monoxide (Al 2 O) was used to identify these chemical intermediates. Time-resolved fluorescence spectra of AlO and Al 2 O were used to observe the temporal evolution in laser-induced Al plasmas and to study their formation in the Al-O 2 chemistry in air.

  17. Quantum chemical evaluation for the stability of liquid sodium containing titanium nanoparticles

    International Nuclear Information System (INIS)

    Suzuki, Ai; Inaba, Kenji; Ishizawa, Yukie; Miura, Ryuji; Hatakeyama, Nozomu; Miyamoto, Akira; Saito, Jun-ichi; Ara, Kuniaki

    2015-01-01

    Recently, liquid sodium containing titanium nanoparticles (LSnanop) have attracted considerable attention. In this study, suspension state of Ti nanoparticle in liquid sodium was quantum chemically evaluated. The atomic interaction between Ti nanoparticles and sodium atoms in the liquid sodium medium was investigated. There were some literatures which gained quantum chemical insight into a nanoparticle with the surrounding sodium atom. However, liquid sodium medium itself together with a Ti nanoparticle under the realistic temperature has not yet been investigated theoretically. To overcome the problem of conventional theoretical method, we applied computationally low-load Tight Binding Quantum Chemical Molecular Dynamics (TB-QCMD) calculation method to investigate the suspension state of the Ti nanoparticle in liquid sodium metal. (author)

  18. Study on chemical reactivity control of liquid sodium. Research program

    International Nuclear Information System (INIS)

    Saito, Jun-ichi; Ara, Kuniaki; Sugiyama, Ken-ichiro; Kitagawa, Hiroshi; Oka, Nobuki; Yoshioka, Naoki

    2007-01-01

    Liquid sodium has the excellent properties as coolant of the fast breeder reactor (FBR). On the other hand, it reacts high with water and oxygen. So an innovative technology to suppress the reactivity is desired. The purpose of this study is to control the chemical reactivity of liquid sodium by dispersing the nanometer-size metallic particles (we call them Nano-particles) into liquid sodium. We focus on the atomic interaction between Nano-particles and sodium atoms. And we try to apply it to suppress the chemical reactivity of liquid sodium. Liquid sodium dispersing Nano-particles is named 'Nano-fluid'. Research programs of this study are the Nano-particles production, the evaluation of reactivity suppression of liquid sodium and the feasibility study to FBR plant. In this paper, the research programs and status are described. The important factors for particle production were understood. In order to evaluate the chemical reactivity of Nano-fluid the research programs were planned. The feasibility of the application of Nano-fluid to the coolant of FBR plant was evaluated preliminarily from the viewpoint of design and operation. (author)

  19. Dimensionless study on dynamics of pressure controlled mechanical ventilation system

    International Nuclear Information System (INIS)

    Shi, Yan; Niu, Jinglong; Cai, Maolin; Xu, Weiqing

    2015-01-01

    Dynamics of mechanical ventilation system can be referred in pulmonary diagnostics and treatments. In this paper, to conveniently grasp the essential characteristics of mechanical ventilation system, a dimensionless model of mechanical ventilation system is presented. For the validation of the mathematical model, a prototype mechanical ventilation system of a lung simulator is proposed. Through the simulation and experimental studies on the dimensionless dynamics of the mechanical ventilation system, firstly, the mathematical model is proved to be authentic and reliable. Secondly, the dimensionless dynamics of the mechanical ventilation system are obtained. Last, the influences of key parameters on the dimensionless dynamics of the mechanical ventilation system are illustrated. The study provides a novel method to study the dynamic of mechanical ventilation system, which can be referred in the respiratory diagnostics and treatment.

  20. Dimensionless study on dynamics of pressure controlled mechanical ventilation system

    Energy Technology Data Exchange (ETDEWEB)

    Shi, Yan; Niu, Jinglong; Cai, Maolin; Xu, Weiqing [Beihang University, Beijing (Korea, Republic of)

    2015-02-15

    Dynamics of mechanical ventilation system can be referred in pulmonary diagnostics and treatments. In this paper, to conveniently grasp the essential characteristics of mechanical ventilation system, a dimensionless model of mechanical ventilation system is presented. For the validation of the mathematical model, a prototype mechanical ventilation system of a lung simulator is proposed. Through the simulation and experimental studies on the dimensionless dynamics of the mechanical ventilation system, firstly, the mathematical model is proved to be authentic and reliable. Secondly, the dimensionless dynamics of the mechanical ventilation system are obtained. Last, the influences of key parameters on the dimensionless dynamics of the mechanical ventilation system are illustrated. The study provides a novel method to study the dynamic of mechanical ventilation system, which can be referred in the respiratory diagnostics and treatment.

  1. Ionic Liquids: Radiation Chemistry, Solvation Dynamics and Reactivity Patterns

    International Nuclear Information System (INIS)

    Wishart, J.F.

    2011-01-01

    Ionic liquids (ILs) are a rapidly expanding family of condensed-phase media with important applications in energy production, nuclear fuel and waste processing, improving the efficiency and safety of industrial chemical processes, and pollution prevention. ILs generally have low volatilities and are combustion-resistant, highly conductive, recyclable and capable of dissolving a wide variety of materials. They are finding new uses in chemical synthesis, catalysis, separations chemistry, electrochemistry and other areas. Ionic liquids have dramatically different properties compared to conventional molecular solvents, and they provide a new and unusual environment to test our theoretical understanding of primary radiation chemistry, charge transfer and other reactions. We are interested in how IL properties influence physical and dynamical processes that determine the stability and lifetimes of reactive intermediates and thereby affect the courses of reactions and product distributions. We study these issues by characterization of primary radiolysis products and measurements of their yields and reactivity, quantification of electron solvation dynamics and scavenging of electrons in different states of solvation. From this knowledge we wish to learn how to predict radiolytic mechanisms and control them or mitigate their effects on the properties of materials used in nuclear fuel processing, for example, and to apply IL radiation chemistry to answer questions about general chemical reactivity in ionic liquids that will aid in the development of applications listed above. Very early in our radiolysis studies it became evident that the slow solvation dynamics of the excess electron in ILs (which vary over a wide viscosity range) increase the importance of pre-solvated electron reactivity and consequently alter product distributions and subsequent chemistry. This difference from conventional solvents has profound effects on predicting and controlling radiolytic yields

  2. Modeling reaction histories to study chemical pathways in condensed phase detonation

    International Nuclear Information System (INIS)

    Scott Stewart, D.; Hernández, Alberto; Lee, Kibaek

    2016-01-01

    The estimation of pressure and temperature histories, which are required to understand chemical pathways in condensed phase explosives during detonation, is discussed. We argue that estimates made from continuum models, calibrated by macroscopic experiments, are essential to inform modern, atomistic-based reactive chemistry simulations at detonation pressures and temperatures. We present easy to implement methods for general equation of state and arbitrarily complex chemical reaction schemes that can be used to compute reactive flow histories for the constant volume, the energy process, and the expansion process on the Rayleigh line of a steady Chapman-Jouguet detonation. A brief review of state-of-the-art of two-component reactive flow models is given that highlights the Ignition and Growth model of Lee and Tarver [Phys. Fluids 23, 2362 (1980)] and the Wide-Ranging Equation of State model of Wescott, Stewart, and Davis [J. Appl. Phys. 98, 053514 (2005)]. We discuss evidence from experiments and reactive molecular dynamic simulations that motivate models that have several components, instead of the two that have traditionally been used to describe the results of macroscopic detonation experiments. We present simplified examples of a formulation for a hypothetical explosive that uses simple (ideal) equation of state forms and detailed comparisons. Then, we estimate pathways computed from two-component models of real explosive materials that have been calibrated with macroscopic experiments.

  3. Supramolecular Systems and Chemical Reactions in Single-Molecule Break Junctions.

    Science.gov (United States)

    Li, Xiaohui; Hu, Duan; Tan, Zhibing; Bai, Jie; Xiao, Zongyuan; Yang, Yang; Shi, Jia; Hong, Wenjing

    2017-04-01

    The major challenges of molecular electronics are the understanding and manipulation of the electron transport through the single-molecule junction. With the single-molecule break junction techniques, including scanning tunneling microscope break junction technique and mechanically controllable break junction technique, the charge transport through various single-molecule and supramolecular junctions has been studied during the dynamic fabrication and continuous characterization of molecular junctions. This review starts from the charge transport characterization of supramolecular junctions through a variety of noncovalent interactions, such as hydrogen bond, π-π interaction, and electrostatic force. We further review the recent progress in constructing highly conductive molecular junctions via chemical reactions, the response of molecular junctions to external stimuli, as well as the application of break junction techniques in controlling and monitoring chemical reactions in situ. We suggest that beyond the measurement of single molecular conductance, the single-molecule break junction techniques provide a promising access to study molecular assembly and chemical reactions at the single-molecule scale.

  4. Dynamics of capillary condensation in lattice gas models of confined fluids: a comparison of dynamic mean field theory with dynamic Monte Carlo simulations.

    Science.gov (United States)

    Edison, John R; Monson, Peter A

    2013-06-21

    This article addresses the accuracy of a dynamic mean field theory (DMFT) for fluids in porous materials [P. A. Monson, J. Chem. Phys. 128, 084701 (2008)]. The theory is used to study the relaxation processes of fluids in pores driven by step changes made to a bulk reservoir in contact with the pore. We compare the results of the DMFT to those obtained by averaging over large numbers of dynamic Monte Carlo (DMC) simulation trajectories. The problem chosen for comparison is capillary condensation in slit pores, driven by step changes in the chemical potential in the bulk reservoir and involving a nucleation process via the formation of a liquid bridge. The principal difference between the DMFT results and DMC is the replacement of a distribution of nucleation times and location along the pore for the formation of liquid bridges by a single time and location. DMFT is seen to yield an otherwise qualitatively accurate description of the dynamic behavior.

  5. A MODELING AND SIMULATION LANGUAGE FOR BIOLOGICAL CELLS WITH COUPLED MECHANICAL AND CHEMICAL PROCESSES.

    Science.gov (United States)

    Somogyi, Endre; Glazier, James A

    2017-04-01

    Biological cells are the prototypical example of active matter. Cells sense and respond to mechanical, chemical and electrical environmental stimuli with a range of behaviors, including dynamic changes in morphology and mechanical properties, chemical uptake and secretion, cell differentiation, proliferation, death, and migration. Modeling and simulation of such dynamic phenomena poses a number of computational challenges. A modeling language describing cellular dynamics must naturally represent complex intra and extra-cellular spatial structures and coupled mechanical, chemical and electrical processes. Domain experts will find a modeling language most useful when it is based on concepts, terms and principles native to the problem domain. A compiler must then be able to generate an executable model from this physically motivated description. Finally, an executable model must efficiently calculate the time evolution of such dynamic and inhomogeneous phenomena. We present a spatial hybrid systems modeling language, compiler and mesh-free Lagrangian based simulation engine which will enable domain experts to define models using natural, biologically motivated constructs and to simulate time evolution of coupled cellular, mechanical and chemical processes acting on a time varying number of cells and their environment.

  6. Chemical kinetic modeling of H{sub 2} applications

    Energy Technology Data Exchange (ETDEWEB)

    Marinov, N.M.; Westbrook, C.K.; Cloutman, L.D. [Lawrence Livermore National Lab., CA (United States)] [and others

    1995-09-01

    Work being carried out at LLNL has concentrated on studies of the role of chemical kinetics in a variety of problems related to hydrogen combustion in practical combustion systems, with an emphasis on vehicle propulsion. Use of hydrogen offers significant advantages over fossil fuels, and computer modeling provides advantages when used in concert with experimental studies. Many numerical {open_quotes}experiments{close_quotes} can be carried out quickly and efficiently, reducing the cost and time of system development, and many new and speculative concepts can be screened to identify those with sufficient promise to pursue experimentally. This project uses chemical kinetic and fluid dynamic computational modeling to examine the combustion characteristics of systems burning hydrogen, either as the only fuel or mixed with natural gas. Oxidation kinetics are combined with pollutant formation kinetics, including formation of oxides of nitrogen but also including air toxics in natural gas combustion. We have refined many of the elementary kinetic reaction steps in the detailed reaction mechanism for hydrogen oxidation. To extend the model to pressures characteristic of internal combustion engines, it was necessary to apply theoretical pressure falloff formalisms for several key steps in the reaction mechanism. We have continued development of simplified reaction mechanisms for hydrogen oxidation, we have implemented those mechanisms into multidimensional computational fluid dynamics models, and we have used models of chemistry and fluid dynamics to address selected application problems. At the present time, we are using computed high pressure flame, and auto-ignition data to further refine the simplified kinetics models that are then to be used in multidimensional fluid mechanics models. Detailed kinetics studies have investigated hydrogen flames and ignition of hydrogen behind shock waves, intended to refine the detailed reactions mechanisms.

  7. Physico-chemical studies of radiation effects in cells: Final report

    International Nuclear Information System (INIS)

    Powers, E.L.

    1987-03-01

    The career of Dr. E.L. Powers, a pioneer in the development of radiobiology, is reviewed. His initial research involved the effects of radiation and certain chemicals on Paramecium, associated ultrastructural studies on protozoan cells, responses of Rickettsia and bacteriophage to irradiation, and the development of techniques for studying bacterial spores. These efforts established the basic radiation biology of the spore and its importance in understanding the effects of free radicals, oxygen, and water. His recent research extended work on the dry spore to the very wet spore and to other selected chemical systems in aqueous suspension. 126 refs., 2 figs

  8. 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.

    2012-07-01

    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 require students to use approaches beyond direct application of LCP. Sample : The questionnaire was administered to 162 students studying their first year of advanced chemistry (age 16/17) in three high achieving London high schools. Design and methods : The students' explanations of reversible chemical systems were inductively coded to identify the explanatory approaches used and interviews with 13 students were used to check for consistency. AS level examination questions on reversible reactions were analysed to identify the types of explanations sought and the students' performance in these examinations was compared to questionnaire answers. Results : 19% of students used a holistic explanatory approach: when the rates of forward and reverse reactions are correctly described, recognising their simultaneous and mutually dependent nature. 36% used a mirrored reactions approach when the connected nature of the forward and reverse reactions is identified, but not their mutual dependency. 42% failed to recognize the interdependence of forward and reverse reactions (reactions not connected approach). Only 4% of marks for AS examination questions on reversible chemical systems asked for responses which went beyond either direct application of LCP or recall of equilibrium knowledge. 37% of students attained an A grade in their AS national examinations. Conclusions : Examinations favour the application of LCP making it possible to obtain the highest grade with little understanding of reversible chemical systems beyond a direct application of this algorithm. Therefore students' understanding may be attenuated so that they are

  9. Engineering Microbial Metabolite Dynamics and Heterogeneity.

    Science.gov (United States)

    Schmitz, Alexander C; Hartline, Christopher J; Zhang, Fuzhong

    2017-10-01

    As yields for biological chemical production in microorganisms approach their theoretical maximum, metabolic engineering requires new tools, and approaches for improvements beyond what traditional strategies can achieve. Engineering metabolite dynamics and metabolite heterogeneity is necessary to achieve further improvements in product titers, productivities, and yields. Metabolite dynamics, the ensemble change in metabolite concentration over time, arise from the need for microbes to adapt their metabolism in response to the extracellular environment and are important for controlling growth and productivity in industrial fermentations. Metabolite heterogeneity, the cell-to-cell variation in a metabolite concentration in an isoclonal population, has a significant impact on ensemble productivity. Recent advances in single cell analysis enable a more complete understanding of the processes driving metabolite heterogeneity and reveal metabolic engineering targets. The authors present an overview of the mechanistic origins of metabolite dynamics and heterogeneity, why they are important, their potential effects in chemical production processes, and tools and strategies for engineering metabolite dynamics and heterogeneity. The authors emphasize that the ability to control metabolite dynamics and heterogeneity will bring new avenues of engineering to increase productivity of microbial strains. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. NMR studies on the structure and dynamics of lac operator DNA

    International Nuclear Information System (INIS)

    Lee, S.C.

    1985-01-01

    Nuclear Magnetic Resonance spectroscopy was used to elucidate the relationships between structure, dynamics and function of the gene regulatory sequence corresponding to the lactose operon operator of Escherichia coli. The length of the DNA fragments examined varied from 13 to 36 base pair, containing all or part of the operator sequence. These DNA fragments are either derived genetically or synthesized chemically. Resonances of the imino protons were assigned by one dimensional inter-base pair nuclear Overhauser enhancement (NOE) measurements. Imino proton exchange rates were measured by saturation recovery methods. Results from the kinetic measurements show an interesting dynamic heterogeneity with a maximum opening rate centered about a GTG/CAC sequence which correlates with the biological function of the operator DNA. This particular three base pair sequence occurs frequently and often symmetrically in prokaryotic nd eukaryotic DNA sites where one anticipates specific protein interaction for gene regulation. The observed sequence dependent imino proton exchange rate may be a reflection of variation of the local structure of regulatory DNA. The results also indicate that the observed imino proton exchange rates are length dependent

  11. Carrier dynamics in silicon nanowires studied using optical-pump terahertz-probe spectroscopy

    Science.gov (United States)

    Beaudoin, Alexandre; Salem, Bassem; Baron, Thierry; Gentile, Pascal; Morris, Denis

    2014-03-01

    The advance of non-contact measurements involving pulsed terahertz radiation presents great interests for characterizing electrical properties of a large ensemble of nanowires. In this work, N-doped and undoped silicon nanowires (SiNWs) grown by chemical vapour deposition (CVD) on quartz substrate were characterized using optical-pump terahertz probe (OPTP) transmission experiments. Our results show that defects and ionized impurities introduced by N-doping the CVD-grown SiNWs tend to reduce the photoexcited carrier lifetime and degrade their conductivity properties. Capture mechanisms by the surface trap states play a key role on the photocarrier dynamics in theses small diameters' (~100 nm) SiNWs and the doping level is found to alter this dynamics. We propose convincing capture and recombination scenarios that explain our OPTP measurements. Fits of our photoconductivity data curves, from 0.5 to 2 THz, using a Drude-plasmon conductivity model allow determining photocarrier mobility values of 190 and 70 cm2/V .s, for the undoped and N-doped NWs samples, respectively.

  12. Chemical Risk Evaluation: A Case Study in an Automotive Air Conditioner Production Facility

    Directory of Open Access Journals (Sweden)

    Tengku Hanidza T.I.

    2010-01-01

    Full Text Available There has been limited knowledge on worker’s exposure to chemicals used in the automotive industries. The purpose of this study is to assess chemical risk and to determine the adequacy of the existing control measures to reduce chemical exposure. A cross sectional survey was conducted in a factory involving installation and servicing of automotive air conditioner units. Qualitative exposure assessment was carried out following the Malaysian Chemical Health Risk Assessment Manual (CHRA. There were 180 employees, 156 workers worked in the production line, which constitutes six work units Tube fin pressed, Brazing, Welding, Final assembly, Piping and Kit II. From the chemical risk evaluation for each work unit, 26 chemical compounds were used. Most of the chemicals were irritants (eye and skin and some were asphyxiants and sensitizers. Based on the work assignment, 93 out of 180 (51.67% of the workers were exposed to chemicals. The highest numbers of workers exposed to chemicals were from the Brazing section (22.22% while the Final Assembly section was the lowest (1.67%. Health survey among the workers showed occurrence of eye irritation, skin irritation, and respiratory irritation, symptoms usually associated with chemical exposure. Using a risk rating matrix, several work process were identified as having ‘significant risk’. For these areas, the workers are at risk of adverse health effects since chemical exposure is not adequately controlled. This study recommends corrective actions be taken in order to control the level of exposure and to provide a safe work environment for workers.

  13. Effects of glycosylation on the conformation and dynamics of O-linked glycoproteins: Carbon-13 NMR studies of ovine submaxillary mucin

    International Nuclear Information System (INIS)

    Gerken, T.A.; Butenhof, K.J.; Shogren, R.

    1989-01-01

    Carbon-13 NMR spectroscopic studies of native and sequentially deglycosylated ovine submaxillary mucin (OSM) have been performed to examine the effects of glycosylation on the conformation and dynamics of the peptide core of O-linked glycoproteins. OSM is a large nonglobular glycoprotein in which nearly one-third of the amino acid residues are Ser and Thr which are glycosylated by the α-Neu-NAc(2-6)α-Ga1NAc- disaccharide. The β-carbon resonances of glycosylated Ser and Thr residues in intact and asialo mucin display considerable chemical shift heterogeneity which, upon the complete removal of carbohydrate, coalesces to single sharp resonances. This chemical shift heterogeneity is due to peptide sequence variability and is proposed to reflect the presence of sequence-dependent conformations of the peptide core. These different conformations are thought to be determined by steric interactions of the Ga1NAc residue with adjacent peptide residues. The absence of chemical shift heterogeneity in apo mucin is taken to indicate a loss in the peptide-carbohydrate steric interactions, consistent with a more relaxed random coiled structure. On the basis of the 13 C relaxation behavior the dynamics of the α-carbons appear to be unique to each amino acid type and glycosylation state. These results are consistent with the changes in molecular dimensions determined by light-scattering techniques for the same series of modified mucins. Taken together, these results further demonstrate that mucins possess a highly expanded conformation that is dominated by steric interactions between the peptide core and the O-linked Ga1NAc residue

  14. Proceedings of "Optical Probes of Dynamics in Complex Environments"

    Energy Technology Data Exchange (ETDEWEB)

    Sension, R; Tokmakoff, A

    2008-04-01

    This document contains the proceedings from the symposium on Optical Probes of Dynamics in Complex Environments, which organized as part of the 235th National Meeting of the American Chemical Society in New Orleans, LA from April 6 to 10, 2008. The study of molecular dynamics in chemical reaction and biological processes using time ƒresolved spectroscopy plays an important role in our understanding of energy conversion, storage, and utilization problems. Fundamental studies of chemical reactivity, molecular rearrangements, and charge transport are broadly supported by the DOE Office of Science because of their role in the development of alternative energy sources, the understanding of biological energy conversion processes, the efficient utilization of existing energy resources, and the mitigation of reactive intermediates in radiation chemistry. In addition, time resolved spectroscopy is central to all of DOEs grand challenges for fundamental energy science. This symposium brought together leaders in the field of ultrafast spectroscopy, including experimentalists, theoretical chemists, and simulators, to discuss the most recent scientific and technological advances. DOE support for this conference was used to help young US and international scientists travel to the meeting. The latest technology in ultrafast infrared, optical, and xray spectroscopy and the scientific advances that these methods enable were covered. Particular emphasis was placed on new experimental methods used to probe molecular dynamics in liquids, solids, interfaces, nanostructured materials, and biomolecules.

  15. [Studies on photo-electron-chemical catalytic degradation of the malachite green].

    Science.gov (United States)

    Li, Ming-yu; Diao, Zeng-hui; Song, Lin; Wang, Xin-le; Zhang, Yuan-ming

    2010-07-01

    A novel two-compartment photo-electro-chemical catalytic reactor was designed. The TiO2/Ti thin film electrode thermally formed was used as photo-anode, and graphite as cathode and a saturated calomel electrode (SCE) as the reference electrode in the reactor. The anode compartment and cathode compartment were connected with the ionic exchange membrane in this reactor. Effects of initial pH, initial concentration of malachite green and connective modes between the anode compartment and cathode compartment on the decolorization efficiency of malachite green were investigated. The degradation dynamics of malachite green was studied. Based on the change of UV-visible light spectrum, the degradation process of malachite green was discussed. The experimental results showed that, during the time of 120 min, the decolouring ratio of the malachite green was 97.7% when initial concentration of malachite green is 30 mg x L(-1) and initial pH is 3.0. The catalytic degradation of malachite green was a pseudo-first order reaction. In the degradation process of malachite green the azo bond cleavage and the conjugated system of malachite green were attacked by hydroxyl radical. Simultaneity, the aromatic ring was oxidized. Finally, malachite green was degraded into other small molecular compounds.

  16. Identification of Chemical Toxicity Using Ontology Information of Chemicals

    Directory of Open Access Journals (Sweden)

    Zhanpeng Jiang

    2015-01-01

    Full Text Available With the advance of the combinatorial chemistry, a large number of synthetic compounds have surged. However, we have limited knowledge about them. On the other hand, the speed of designing new drugs is very slow. One of the key causes is the unacceptable toxicities of chemicals. If one can correctly identify the toxicity of chemicals, the unsuitable chemicals can be discarded in early stage, thereby accelerating the study of new drugs and reducing the R&D costs. In this study, a new prediction method was built for identification of chemical toxicities, which was based on ontology information of chemicals. By comparing to a previous method, our method is quite effective. We hope that the proposed method may give new insights to study chemical toxicity and other attributes of chemicals.

  17. Cooperative unfolding of apolipoprotein A-1 induced by chemical denaturation.

    Science.gov (United States)

    Eckhardt, D; Li-Blatter, X; Schönfeld, H-J; Heerklotz, H; Seelig, J

    2018-05-25

    Apolipoprotein A-1 (Apo A-1) plays an important role in lipid transfer and obesity. Chemical unfolding of α-helical Apo A-1 is induced with guanidineHCl and monitored with differential scanning calorimetry (DSC) and CD spectroscopy. The unfolding enthalpy and the midpoint temperature of unfolding decrease linearly with increasing guanidineHCl concentration, caused by the weak binding of denaturant. At room temperature, binding of 50-60 molecules guanidineHCl leads to a complete Apo A-1 unfolding. The entropy of unfolding decreases to a lesser extent than the unfolding enthalpy. Apo A-1 chemical unfolding is a dynamic multi-state equilibrium that is analysed with the Zimm-Bragg theory modified for chemical unfolding. The chemical Zimm-Bragg theory predicts the denaturant binding constant K D and the protein cooperativity σ. Chemical unfolding of Apo A-1 is two orders of magnitude less cooperative than thermal unfolding. The free energy of thermal unfolding is ~0.2 kcal/mol per amino acid residue and ~1.0 kcal/mol for chemical unfolding at room temperature. The Zimm-Bragg theory calculates conformational probabilities and the chemical Zimm-Bragg theory predicts stretches of α-helical segments in dynamic equilibrium, unfolding and refolding independently and fast. Copyright © 2018 The Authors. Published by Elsevier B.V. All rights reserved.

  18. The photodissociation and reaction dynamics of vibrationally excited molecules

    Energy Technology Data Exchange (ETDEWEB)

    Crim, F.F. [Univ. of Wisconsin, Madison (United States)

    1993-12-01

    This research determines the nature of highly vibrationally excited molecules, their unimolecular reactions, and their photodissociation dynamics. The goal is to characterize vibrationally excited molecules and to exploit that understanding to discover and control their chemical pathways. Most recently the author has used a combination of vibrational overtone excitation and laser induced fluorescence both to characterize vibrationally excited molecules and to study their photodissociation dynamics. The author has also begun laser induced grating spectroscopy experiments designed to obtain the electronic absorption spectra of highly vibrationally excited molecules.

  19. Study on dynamic performance of SOFC

    Science.gov (United States)

    Zhan, Haiyang; Liang, Qianchao; Wen, Qiang; Zhu, Runkai

    2017-05-01

    In order to solve the problem of real-time matching of load and fuel cell power, it is urgent to study the dynamic response process of SOFC in the case of load mutation. The mathematical model of SOFC is constructed, and its performance is simulated. The model consider the influence factors such as polarization effect, ohmic loss. It also takes the diffusion effect, thermal effect, energy exchange, mass conservation, momentum conservation. One dimensional dynamic mathematical model of SOFC is constructed by using distributed lumped parameter method. The simulation results show that the I-V characteristic curves are in good agreement with the experimental data, and the accuracy of the model is verified. The voltage response curve, power response curve and the efficiency curve are obtained by this way. It lays a solid foundation for the research of dynamic performance and optimal control in power generation system of high power fuel cell stack.

  20. LCA of Chemicals and Chemical Products

    DEFF Research Database (Denmark)

    Fantke, Peter; Ernstoff, Alexi

    2018-01-01

    This chapter focuses on the application of Life Cycle Assessment (LCA) to evaluate the environmental performance of chemicals as well as of products and processes where chemicals play a key role. The life cycle stages of chemical products, such as pharmaceuticals drugs or plant protection products......, are discussed and differentiated into extraction of abiotic and biotic raw materials, chemical synthesis and processing, material processing, product manufacturing, professional or consumer product use, and finally end-of-life . LCA is discussed in relation to other chemicals management frameworks and concepts...... including risk assessment , green and sustainable chemistry , and chemical alternatives assessment. A large number of LCA studies focus on contrasting different feedstocks or chemical synthesis processes, thereby often conducting a cradle to (factory) gate assessment. While typically a large share...

  1. Chemical reactions in the presence of surface modulation and stirring

    OpenAIRE

    Kamhawi, Khalid; Náraigh, Lennon Ó

    2009-01-01

    We study the dynamics of simple reactions where the chemical species are confined on a general, time-modulated surface, and subjected to externally-imposed stirring. The study of these inhomogeneous effects requires a model based on a reaction-advection-diffusion equation, which we derive. We use homogenization methods to show that up to second order in a small scaling parameter, the modulation effects on the concentration field are asymptotically equivalent for systems with or without stirri...

  2. Field studies and modeling of chemical processes in the unsaturated zone

    International Nuclear Information System (INIS)

    Polzer, W.L.; Fuentes, H.R.

    1985-01-01

    Technical assistance is being provided to Nuclear Materials Safety and Safeguards of the Nuclear Regulatory Commission to evaluate the validity of several guidelines listed in 10 CFR Part 61 for the future burial of low-level radioactive waste. Those guidelines include the requirement that the burial site shall be capable of being modeled. Both laboratory- and field-scale studies are being conducted under unsaturated moisture conditions and under steady-state and unsteady-state flow conditions. This paper reviews the kinds of present experiments in low-level radioactive waste disposal in development at the Los Alamos National Laboratory. Major emphasis is on some of the initial analyses of data for laboratory sorption experiments and for field transport tests. Brief reference is made to leaching and transport studies. Laboratory batch equilibrium sorption studies suggest that adsorption of nonconservative tracers can be described in terms of two empirical constants; one gives an indication of the average K/sub d/ for all adsorption sites and the other gives an indication of the spread of individual K/sub d/'s about the average K/sub d/. This information can be translated into a ''chemical dispersion'' under dynamic flow and equilibrium sorption conditions that is in addition to the traditionally accepted physical dispersion. Laboratory nonequilibrium sorption studies suggest that nonequilibrium models may be needed to model the transport of the nonconservative tracers cobalt and cesium; equilibrium models should be suitable to model strontium transport. Analyses from field-scale studies indicate that conservative tracers can reasonably be modeled with a one-dimensional advective-dispersive equation for steady flow. 12 figs., 1 tab

  3. Integrating atomistic molecular dynamics simulations, experiments and network analysis to study protein dynamics: strength in unity

    Directory of Open Access Journals (Sweden)

    Elena ePapaleo

    2015-05-01

    Full Text Available In the last years, we have been observing remarkable improvements in the field of protein dynamics. Indeed, we can now study protein dynamics in atomistic details over several timescales with a rich portfolio of experimental and computational techniques. On one side, this provides us with the possibility to validate simulation methods and physical models against a broad range of experimental observables. On the other side, it also allows a complementary and comprehensive view on protein structure and dynamics. What is needed now is a better understanding of the link between the dynamic properties that we observe and the functional properties of these important cellular machines. To make progresses in this direction, we need to improve the physical models used to describe proteins and solvent in molecular dynamics, as well as to strengthen the integration of experiments and simulations to overcome their own limitations. Moreover, now that we have the means to study protein dynamics in great details, we need new tools to understand the information embedded in the protein ensembles and in their dynamic signature. With this aim in mind, we should enrich the current tools for analysis of biomolecular simulations with attention to the effects that can be propagated over long distances and are often associated to important biological functions. In this context, approaches inspired by network analysis can make an important contribution to the analysis of molecular dynamics simulations.

  4. 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...

  5. Computational fluid dynamics simulation for chemical looping combustion of coal in a dual circulation fluidized bed

    International Nuclear Information System (INIS)

    Su, Mingze; Zhao, Haibo; Ma, Jinchen

    2015-01-01

    Highlights: • CFD simulation of a 5 kW_t_h CLC reactor of coal was conducted. • Gas leakage, flow pattern and combustion efficiency of the reactor was analyzed. • Optimal condition was achieved based on operation characteristics understanding. - Abstract: A dual circulation fluidized bed system is widely accepted for chemical looping combustion (CLC) for enriching CO_2 from the utilization of fossil fuels. Due to the limitations of the measurement, the details of multiphase reactive flows in the interconnected fluidized bed reactors are difficult to obtain. Computational Fluid Dynamics (CFD) simulation provides a promising method to understand the hydrodynamics, chemical reaction, and heat and mass transfers in CLC reactors, which are very important for the rational design, optimal operation, and scaling-up of the CLC system. In this work, a 5 kW_t_h coal-fired CLC dual circulation fluidized bed system, which was developed by our research group, was first simulated for understanding gas leakage, flow pattern and combustion efficiency. The simulation results achieved good agreement with the experimental measurements, which validates the simulation model. Subsequently, to improve the combustion efficiency, a new operation condition was simulated by increasing the reactor temperature and decreasing the coal feeding. An improvement in the combustion efficiency was attained, and the simulation results for the new operation condition were also validated by the experimental measurements in the same CLC combustor. All of the above processes demonstrated the validity and usefulness of the simulation results to improve the CLC reactor operation.

  6. Solar dynamic power system definition study

    Science.gov (United States)

    Wallin, Wayne E.; Friefeld, Jerry M.

    1988-01-01

    The solar dynamic power system design and analysis study compared Brayton, alkali-metal Rankine, and free-piston Stirling cycles with silicon planar and GaAs concentrator photovoltaic power systems for application to missions beyond the Phase 2 Space Station level of technology for all power systems. Conceptual designs for Brayton and Stirling power systems were developed for 35 kWe and 7 kWe power levels. All power systems were designed for 7-year end-of-life conditions in low Earth orbit. LiF was selected for thermal energy storage for the solar dynamic systems. Results indicate that the Stirling cycle systems have the highest performance (lowest weight and area) followed by the Brayton cycle, with photovoltaic systems considerably lower in performance. For example, based on the performance assumptions used, the planar silicon power system weight was 55 to 75 percent higher than for the Stirling system. A technology program was developed to address areas wherein significant performance improvements could be realized relative to the current state-of-the-art as represented by Space Station. In addition, a preliminary evaluation of hardenability potential found that solar dynamic systems can be hardened beyond the hardness inherent in the conceptual designs of this study.

  7. Studies of radiation and chemical toxicity. Progress report

    International Nuclear Information System (INIS)

    1986-01-01

    Annual report for the Studies of Radiation and Chemical Toxicity Program at the University of Rochester is presented. Progress is reported on four projects: Neurobehavorial Toxicity of Organometallic Fuel Additives, Mechanisms of Permanent and Delayed Pathologic Effects of Ionizing Radiation, Solid State Radiation Chemistry of the DNA Backbone, and Pulmonary Biochemistry

  8. 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…

  9. Si(111)-7 x 7: First-principles study of dynamics

    International Nuclear Information System (INIS)

    Stich, I.; Kohanoff, J.; Terakura, K.

    1995-12-01

    We present a large-scale fully ab initio molecular dynamics study of dynamical properties of the Takayanagi reconstructed Si(111)-7 x 7 surface. The simulation reproduces well the experimentally determined features of the phonon spectra and clarifies their nature and origin. Correlations are found between these dynamical properties and elements of the local electronic structure of the adatom dangling bonds. We find evidence for important anharmonic effects of below room temperature. Use of non-traditional signal-processing methods allows for a considerable insight into the details of the dynamics from a short-duration molecular dynamics trajectory. Results of this analysis significantly extend/modify the results of the previous studies based on more simplified models. (author). 29 refs, 12 figs, 1 tab

  10. Non-allergic cutaneous reactions in airborne chemical sensitivity--a population based study.

    Science.gov (United States)

    Berg, Nikolaj Drimer; Linneberg, Allan; Thyssen, Jacob Pontoppidan; Dirksen, Asger; Elberling, Jesper

    2011-06-01

    Multiple chemical sensitivity (MCS) is characterised by adverse effects due to exposure to low levels of chemical substances. The aetiology is unknown, but chemical related respiratory symptoms have been found associated with positive patch test. The purpose of this study was to investigate the relationship between cutaneous reactions from patch testing and self-reported severity of chemical sensitivity to common airborne chemicals. A total of 3460 individuals participating in a general health examination, Health 2006, were patch tested with allergens from the European standard series and screened for chemical sensitivity with a standardised questionnaire dividing the participants into four severity groups of chemical sensitivity. Both allergic and non-allergic cutaneous reactions--defined as irritative, follicular, or doubtful allergic reactions--were analysed in relationship with severity of chemical sensitivity. Associations were controlled for the possible confounding effects of sex, age, asthma, eczema, atopic dermatitis, psychological and social factors, and smoking habits. In unadjusted analyses we found associations between allergic and non-allergic cutaneous reactions on patch testing and the two most severe groups of self-reported sensitivity to airborne chemicals. When adjusting for confounding, associations were weakened, and only non-allergic cutaneous reactions were significantly associated with individuals most severely affected by inhalation of airborne chemicals (odds ratio = 2.5, p = 0.006). Our results suggest that individuals with self-reported chemical sensitivity show increased non-allergic cutaneous reactions based on day 2 readings of patch tests. Copyright © 2011 Elsevier GmbH. All rights reserved.

  11. Factors associated with chemical burns in Zhejiang province, China: An epidemiological study

    Directory of Open Access Journals (Sweden)

    Jiang Rui M

    2011-09-01

    Full Text Available Abstract Background Work-related burns are common among occupational injuries. Zhejiang Province is an industrial area with a high incidence of chemical burns. We aimed to survey epidemiological features of chemical burns in Zhejiang province to determine associated factors and acquire data for developing a strategy to prevent and treat chemical burns. Methods Questionnaires were developed, reviewed and validated by experts, and sent to 25 hospitals in Zhejiang province to prospectively collect data of 492 chemical burn patients admitted during one year from Sept. 1, 2008 to Aug. 31, 2009. Questions included victims' characteristics and general condition, injury location, causes of accident, causative chemicals, total body surface area burn, concomitant injuries, employee safety training, and awareness level of protective measures. Surveys were completed for each of burn patients by burn department personnel who interviewed the hospitalized patients. Results In this study, 417 victims (87.61% got chemical burn at work, of which 355 victims (74.58% worked in private or individual enterprises. Most frequent chemicals involved were hydrofluoric acid and sulfuric acid. Main causes of chemical injury accidents were inappropriate operation of equipment or handling of chemicals and absence of or failure to use effective individual protection. Conclusions Most chemical burns are preventable occupational injuries that can be attributed to inappropriate operation of equipment or handling of chemicals, lack of employee awareness about appropriate action and lack of effective protective equipment and training. Emphasis on safety education and protection for workers may help protect workers and prevent chemical burns.

  12. Study on stainless steel electrode based on dynamic aluminum liquid corrosion mechanism.

    Science.gov (United States)

    Hou, Hua; Yang, Ruifeng

    2009-01-01

    Scanning electrion microscope (SEM) was performed for investigations on the corrosion mechanism of stainless steel electrode in dynamic melting aluminum liquid. Microstructures and composition analysis was made by electron probe analysis (EPA) combined with metallic phase analysis. It can be concluded that the corrosion process is mainly composed of physical corrosion (flowing and scouring corrosion) and chemical corrosion (forming FeAl and Fe2Al5) and the two mechanisms usually exist simultaneously. The corrosion interface thickness is about 10 μm, which is different to usual interface width of hundreds μm in the static melting Al with iron matrix.

  13. Studying Chemical Reactions, One Bond at a Time, with Single Molecule AFM Techniques

    Science.gov (United States)

    Fernandez, Julio M.

    2008-03-01

    The mechanisms by which mechanical forces regulate the kinetics of a chemical reaction are unknown. In my lecture I will demonstrate how we use single molecule force-clamp spectroscopy and protein engineering to study the effect of force on the kinetics of thiol/disulfide exchange. Reduction of disulfide bond via the thiol/disulfide exchange chemical reaction is crucial in regulating protein function and is of common occurrence in mechanically stressed proteins. While reduction is thought to proceed through a substitution nucleophilic bimolecular (SN2) reaction, the role of a mechanical force in modulating this chemical reaction is unknown. We apply a constant stretching force to single engineered disulfide bonds and measure their rate of reduction by dithiothreitol (DTT). We find that while the reduction rate is linearly dependent on the concentration of DTT, it is exponentially dependent on the applied force, increasing 10-fold over a 300 pN range. This result predicts that the disulfide bond lengthens by 0.34 å at the transition state of the thiol/disulfide exchange reaction. In addition to DTT, we also study the reduction of the engineered disulfide bond by the E. coli enzyme thioredoxin (Trx). Thioredoxins are enzymes that catalyze disulfide bond reduction in all organisms. As before, we apply a mechanical force in the range of 25-450 pN to the engineered disulfide bond substrate and monitor the reduction of these bonds by individual enzymes. In sharp contrast with the data obtained with DTT, we now observe two alternative forms of the catalytic reaction, the first requiring a reorientation of the substrate disulfide bond, causing a shortening of the substrate polypeptide by 0.76±0.07 å, and the second elongating the substrate disulfide bond by 0.21±0.01 å. These results support the view that the Trx active site regulates the geometry of the participating sulfur atoms, with sub-ångström precision, in order to achieve efficient catalysis. Single molecule

  14. Exploring Chemical Equilibrium with Poker Chips: A General Chemistry Laboratory Exercise

    Science.gov (United States)

    Bindel, Thomas H.

    2012-01-01

    A hands-on laboratory exercise at the general chemistry level introduces students to chemical equilibrium through a simulation that uses poker chips and rate equations. More specifically, the exercise allows students to explore reaction tables, dynamic chemical equilibrium, equilibrium constant expressions, and the equilibrium constant based on…

  15. Challenges to studying the health effects of early life environmental chemical exposures on children's health.

    Science.gov (United States)

    Braun, Joseph M; Gray, Kimberly

    2017-12-01

    Epidemiological studies play an important role in quantifying how early life environmental chemical exposures influence the risk of childhood diseases. These studies face at least four major challenges that can produce noise when trying to identify signals of associations between chemical exposure and childhood health. Challenges include accurately estimating chemical exposure, confounding from causes of both exposure and disease, identifying periods of heightened vulnerability to chemical exposures, and determining the effects of chemical mixtures. We provide recommendations that will aid in identifying these signals with more precision.

  16. [Study on the chemical constituents of Buddleja purdomii].

    Science.gov (United States)

    Zhang, Yinghua; Li, Chong; Zhang, Chengzhong; Tao, Baoquan

    2005-11-01

    To study the chemical constituents of Buddleja purdomii W. W Smith. The constituents were isolated and purified by various chromatographic methods and structurally identified by spectral analysis. 4 compounds were obtained as cryptomeridiol (I), aucubin (II), galactilol (III), daucosterol (IV). All these compounds are obtained from this plant for the first time.

  17. Use of batch and column methodologies to assess utility waste leaching and subsurface chemical attenuation

    International Nuclear Information System (INIS)

    Zachara, J.M.; Streile, G.P.

    1991-05-01

    Waste leaching and chemical attenuation involve geochemical reactions between immobile solid surfaces in the waste or in other porous media and dissolved solutes in the mobile fluid phase. Because the geochemical reactions occur along with water flow, the question often arises whether waste leaching and chemical attenuation are best studied under static or dynamic conditions. To answer this question, the scientific literature was reviewed to identify how static (batch) and dynamic (column) approaches have been applied to obtain data on waste leaching and chemical attenuation and the types of information each technique has provided. This review made it possible to both (1) assess the specific merits of the batch and column experimental techniques and (2) develop an integrated research strategy for employing these techniques to quantify leaching and chemical attenuation processes under conditions relevant to the field. This review led to the conclusion that batch systems are best suited to systematically establishing the specific geochemical reactions involved in leaching and attenuation, obtaining thermodynamic and kinetic constants, and identifying the manifestation of these reactions in wastes or natural subsurface materials. 184 refs., 5 figs., 4 tabs

  18. Model for the dynamic study of AC contactors

    Energy Technology Data Exchange (ETDEWEB)

    Corcoles, F.; Pedra, J.; Garrido, J.P.; Baza, R. [Dep. d' Eng. Electrica ETSEIB. UPC, Barcelona (Spain)

    2000-08-01

    This paper proposes a model for the dynamic analysis of AC contactors. The calculation algorithm and implementation are discussed. The proposed model can be used to study the influence of the design parameters and the supply in their dynamic behaviour. The high calculation speed of the implemented algorithm allows extensive ranges of parameter variations to be analysed. (orig.)

  19. A dynamic study on the sulfuric acid distillation column for VHTR-assisted hydrogen production systems

    International Nuclear Information System (INIS)

    Youngjoon, Shin; Heesung, Shin; Jiwoon, Jang; Kiyoung, Lee; Jonghwa, Chang

    2007-01-01

    The sulfur-iodine (SI) cycle and the Westinghouse sulfur hybrid cycle coupled to a very high temperature gas-cooled reactor (VHTR) are well known as a feasible technology to produce hydrogen. The concentration of the sulfuric acid solution and its decomposition are essential parts in both cycles. In this paper, the thermophysical properties which are the boiling point, latent heat, and the partial pressures of water, sulfuric acid, and sulfur trioxide have been correlated as a function of the sulfuric acid concentration for the H 2 SO 4 and H 2 O binary chemical system, based on the data in Perry's chemical engineers' hand-book and other experimental data. By using these thermophysical correlations, a dynamic analysis of a sulfuric acid distillation column has been performed to establish the column design requirements and its optimum operation condition. From the results of the dynamic analysis, an optimized column system is anticipated for a distillation column equipped with 2 ideal plates and a second plate feeding system from the bottom plate. The effects of the hold-up of the re-boiler and the reflux ratio from the top product stream on the elapsing time when the system progresses toward a steady state have been analyzed. (authors)

  20. Application of single photon ECT for dynamic study

    International Nuclear Information System (INIS)

    Mukai, T.; Ishii, Y.; Tamaki, N.

    1982-01-01

    Feasibility of dynamic study in a form of ECT using a rotating gamma camera was evaluated. Since it takes longer one around time sampling, application for the dynamic study is limited under following conditions; 1) physiological gated process, 2) slow clearance process, 3) physiological steady state process. The gated study was applicated for heart pumping action synchronized with ECG. The ECG gated heart ECT either of blood pool or myocardium was useful to reveal a subtle wall motion abnormalities in a tomographic plane, even when a planar imaging failed to reveal it. As for slow dynamic process of tracer, an excretion process of hepatobiliary agent, was subjected to be analyzed in order to calculate clearance rate at each pixel. As for steady state process, an ECT of regional celebral blood flow (rCBF) was investigated during continuous infusion into intracarotid artery. All of these technique were proved to have a clinical feasibility and to potentiate usefulness of the single photon ECT (SPECT)

  1. Development of a Procedure to Apply Detailed Chemical Kinetic Mechanisms to CFD Simulations as Post Processing

    DEFF Research Database (Denmark)

    Skjøth-Rasmussen, Martin Skov; Glarborg, Peter; Jensen, Anker

    2003-01-01

    mechanism. It involves post-processing of data extracted from computational fluid dynamics simulations. Application of this approach successfully describes combustion chemistry in a standard swirl burner, the so-called Harwell furnace. Nevertheless, it needs validation against more complex combustion models......It is desired to make detailed chemical kinetic mechanisms applicable to the complex geometries of practical combustion devices simulated with computational fluid dynamics tools. This work presents a novel general approach to combining computational fluid dynamics and a detailed chemical kinetic...

  2. Behavior of chemicals in the seawater column by shadowscopy

    Science.gov (United States)

    Fuhrer, Mélanie; Aprin, Laurent; Le Floch, Stéphane; Slangen, Pierre; Dusserre, Gilles

    2012-10-01

    Ninety percent of the Global Movement of Goods transit by ship. The transportation of HNS (Hazardous and Noxious Substances) in bulk highly increases with the tanker traffic. The huge volume capacities induce a major risk of accident involving chemicals. Among the latest accidents, many have led to vessels sinking (Ievoli Sun, 2000 - ECE, 2006). In case of floating substances, liquid release in depth entails an ascending two phase flow. The visualization of that flow is complex. Indeed, liquid chemicals have mostly a refractive index close to water, causing difficulties for the assessment of the two phase medium behavior. Several physics aspects are points of interest: droplets characterization (shape evolution and velocity), dissolution kinetics and hydrodynamic vortices. Previous works, presented in the 2010 Speckle conference in Brazil, employed Dynamic Speckle Interferometry to study Methyl Ethyl Ketone (MEK) dissolution in a 15 cm high and 1 cm thick water column. This paper deals with experiments achieved with the Cedre Experimental Column (CEC - 5 m high and 0.8 m in diameter). As the water thickness has been increased, Dynamic Speckle Interferometry results are improved by shadowscopic measurements. A laser diode is used to generate parallel light while high speed imaging records the products rising. Two measurements systems are placed at the bottom and the top of the CEC. The chemical class of pollutant like floaters, dissolvers (plume, trails or droplets) has been then identified. Physics of the two phase flow is presented and shows up the dependence on chemicals properties such as interfacial tension, viscosity and density. Furthermore, parallel light propagation through this disturbed medium has revealed trailing edges vortices for some substances (e.g. butanol) presenting low refractive index changes.

  3. Study of a spur gear dynamic behavior in transient regime

    Science.gov (United States)

    Khabou, M. T.; Bouchaala, N.; Chaari, F.; Fakhfakh, T.; Haddar, M.

    2011-11-01

    In this paper the dynamic behavior of a single stage spur gear reducer in transient regime is studied. Dynamic response of the single stage spur gear reducer is investigated at different rotating velocities. First, gear excitation is induced by the motor torque and load variation in addition to the fluctuation of meshing stiffness due to the variation of input rotational speed. Then, the dynamic response is computed using the Newmark method. After that, a parameter study is made on spur gear powered in the first place by an electric motor and in the second place by four strokes four cylinders diesel engine. Dynamic responses come to confirm a significant influence of the transient regime on the dynamic behavior of a gear set, particularly in the case of engine acyclism condition.

  4. Non-invasive estimation of dissipation from non-equilibrium fluctuations in chemical reactions.

    Science.gov (United States)

    Muy, S; Kundu, A; Lacoste, D

    2013-09-28

    We show how to extract an estimate of the entropy production from a sufficiently long time series of stationary fluctuations of chemical reactions. This method, which is based on recent work on fluctuation theorems, is direct, non-invasive, does not require any knowledge about the underlying dynamics and is applicable even when only partial information is available. We apply it to simple stochastic models of chemical reactions involving a finite number of states, and for this case, we study how the estimate of dissipation is affected by the degree of coarse-graining present in the input data.

  5. [Study on the chemical constituent from Buddleja purdomii].

    Science.gov (United States)

    Gao, Yan; Li, Chong; Zhang, Chengzhong; Xu, Yourui; Tao, Baoquan

    2004-05-01

    To study the chemical constituents from Buddleja purdomii W. W. Smith. The constituents were isolated and purified by various chromatographic methods and structurally identified by spectral analysis. 4 compounds were identified as vanillin (I), vanillic acid (II), acteoside (III), acteoside isomer (IV). All these compounds were obtained from this plant for the first time.

  6. Health Risk Assessment of Harmful Chemicals: Case Study in a Petrochemical Industry

    Directory of Open Access Journals (Sweden)

    M. Motovagheh

    2011-01-01

    Full Text Available Background and aims In the most chemical process industries, workers are exposed to various chemicals and working with these chemicals without considering safety and health considerations can lead to different harmful symptoms. For deciding about control measures and reducing risk to acceptable level , it is necessary to assess the health risk of exposing to harmful chemicals by aid of specific risk assessment techniques in the process industries. The purpose of this study was to assess the health risks arising from the exposures to chemicals in a petrochemical industry.  methods A simple and applied method was used for health risk assessment of chemicals in a petrochemical industry. Firstly job tasks and work process were determined and then different chemicals in each tasks identified and risk ranking was calculated in each job task by aid of hazard and exposure rate.   Results The result showed that workers are exposed to 10 chemicals including Methyl ethyl ketone, Epichlorohydrin, Sulfuric acid, Phenol, Chlorobenzene, Toluene, Isopropanol, Methylene chloride, Chlorideric Acid and Acetone during their work in plant. From these chemicals, the highest risk level was for Epichlorohydrin in the jobs of tank and utility operations and maintenance workers. The next high risk level was for Epichlorohydrin in technical inspecting and Methyl ethyl ketone in Tank and utility operations operator.     Conclusion Hazard information and monitoring data of chemical agents in the chemical industries can be used for assessing health risks from exposures to chemicals and ranking jobs by their risk level. These data can be used for resource allocation for control measures and reducing risk level to acceptable level.    

  7. Chemical-Free Technique to Study the Ultrastructure of Primary Cilium.

    Science.gov (United States)

    Mohieldin, Ashraf M; AbouAlaiwi, Wissam A; Gao, Min; Nauli, Surya M

    2015-11-02

    A primary cilium is a hair-like structure with a width of approximately 200 nm. Over the past few decades, the main challenge in the study of the ultrastructure of cilia has been the high sensitivity of cilia to chemical fixation, which is required for many imaging techniques. In this report, we demonstrate a combined high-pressure freezing (HPF) and freeze-fracture transmission electron microscopy (FFTEM) technique to examine the ultrastructure of a cilium. Our objective is to develop an optimal high-resolution imaging approach that preserves cilia structures in their best natural form without alteration of cilia morphology by chemical fixation interference. Our results showed that a cilium has a swelling-like structure (termed bulb), which was previously considered a fixation artifact. The intramembrane particles observed via HPF/FFTEM indicated the presence of integral membrane proteins and soluble matrix proteins along the ciliary bulb, which is part of an integral structure within the ciliary membrane. We propose that HPF/FFTEM is an important and more suitable chemical-free method to study the ultrastructure of primary cilia.

  8. Dynamic Model of an Ammonia Synthesis Reactor Based on Open Information

    OpenAIRE

    Jinasena, Asanthi; Lie, Bernt; Glemmestad, Bjørn

    2016-01-01

    Ammonia is a widely used chemical, hence the ammonia manufacturing process has become a standard case study in the scientific community. In the field of mathematical modeling of the dynamics of ammonia synthesis reactors, there is a lack of complete and well documented models. Therefore, the main aim of this work is to develop a complete and well documented mathematical model for observing the dynamic behavior of an industrial ammonia synthesis reactor system. The model is complete enough to ...

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

    KAUST Repository

    Suleimanov, Yu.V.; Allen, J.W.; Green, W.H.

    2013-01-01

    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.

  11. Chemistry and Chemical Equilibrium Dynamics of BMAA and Its Carbamate Adducts.

    Science.gov (United States)

    Diaz-Parga, Pedro; Goto, Joy J; Krishnan, V V

    2018-01-01

    Beta-N-methylamino-L-alanine (BMAA) has been demonstrated to contribute to the onset of the ALS/Parkinsonism-dementia complex (ALS/PDC) and is implicated in the progression of other neurodegenerative diseases. While the role of BMAA in these diseases is still debated, one of the suggested mechanisms involves the activation of excitatory glutamate receptors. In particular, the excitatory effects of BMAA are shown to be dependent on the presence of bicarbonate ions, which in turn forms carbamate adducts in physiological conditions. The formation of carbamate adducts from BMAA and bicarbonate is similar to the formation of carbamate adducts from non-proteinogenic amino acids. Structural, chemical, and biological information related to non-proteinogenic amino acids provide insight into the formation of and possible neurological action of BMAA. This article reviews the carbamate formation of BMAA in the presence of bicarbonate ions, with a particular focus on how the chemical equilibrium of BMAA carbamate adducts may affect the molecular mechanism of its function. Highlights of nuclear magnetic resonance (NMR)-based studies on the equilibrium process between free BMAA and its adducts are presented. The role of divalent metals on the equilibrium process is also explored. The formation and the equilibrium process of carbamate adducts of BMAA may answer questions on their neuroactive potency and provide strong motivation for further investigations into other toxic mechanisms.

  12. A study of the HEB longitudinal dynamics

    International Nuclear Information System (INIS)

    Larson, D.J.

    1993-12-01

    A study of the High Energy Booster (HEB) longitudinal dynamics is presented. Full derivations of ramp dependent longitudinal variables are given. The formulas assume that the input magnetic field and beam longitudinal emittance are known as a function of time, and that either the rf voltage or the rf bucket area are known as a function of time. Once these three inputs are specified, the formulas can be used to calculate values for all other longitudinal dynamics variables. The formulas have been incorporated into a single computer code named ELVIRA: Evaluation of Longitudinal Variables in Relativistic Accelerators. The ELVIRA code is documented here in detail. The ELVIRA code is used under two initial longitudinal emittance assumptions to plot ramp functions for the longitudinal dynamics design of the HEB as of May 5, 1992

  13. A national population study of the prevalence of multiple chemical sensitivity.

    Science.gov (United States)

    Caress, Stanley M; Steinemann, Anne C

    2004-06-01

    The authors conducted a telephone survey of 1054 randomly selected individuals within the continental United States to determine the prevalence of chemical hypersensitivity and the medical diagnosis of multiple chemical sensitivity (MCS) in the American population. The etiology and symptomatology of MCS also were investigated. Results produced a 95% confidence level and a +/-3% margin of error. The authors found that 11.2% of Americans reported an unusual hypersensitivity to common chemical products such as perfume, fresh paint, pesticides, and other petrochemical-based substances, and 2.5% reported they had been medically diagnosed with MCS. Additionally, 31.1% of those sampled reported adverse reactions to fragranced products, and 17.6% experienced breathing difficulties and other health problems when exposed to air fresheners. Although chemical hypersensitivity was more common in women, it affected individuals in all demographic groups studied.

  14. Dynamic Modeling of Process Technologies for Closed-Loop Water Recovery Systems

    Science.gov (United States)

    Allada, Rama Kumar; Lange, Kevin E.; Anderson, Molly S.

    2012-01-01

    Detailed chemical process simulations are a useful tool in designing and optimizing complex systems and architectures for human life support. Dynamic and steady-state models of these systems help contrast the interactions of various operating parameters and hardware designs, which become extremely useful in trade-study analyses. NASA s Exploration Life Support technology development project recently made use of such models to compliment a series of tests on different waste water distillation systems. This paper presents dynamic simulations of chemical process for primary processor technologies including: the Cascade Distillation System (CDS), the Vapor Compression Distillation (VCD) system, the Wiped-Film Rotating Disk (WFRD), and post-distillation water polishing processes such as the Volatiles Removal Assembly (VRA). These dynamic models were developed using the Aspen Custom Modeler (Registered TradeMark) and Aspen Plus(Registered TradeMark) process simulation tools. The results expand upon previous work for water recovery technology models and emphasize dynamic process modeling and results. The paper discusses system design, modeling details, and model results for each technology and presents some comparisons between the model results and available test data. Following these initial comparisons, some general conclusions and forward work are discussed.

  15. Real-time chemical characterization of atmospheric particulate matter in China: A review

    Science.gov (United States)

    Li, Yong Jie; Sun, Yele; Zhang, Qi; Li, Xue; Li, Mei; Zhou, Zhen; Chan, Chak K.

    2017-06-01

    Atmospheric particulate matter (PM) pollution has become a major health threat accompanying the rapid economic development in China. For decades, filter-based offline chemical analyses have been the most widely adopted means to investigate PM and have provided much information for understanding this type of pollution in China. However, offline analyses have low time resolutions and the chemical information thus obtained fail to reflect the dynamic nature of the sources and the rapid processes leading to the severe PM pollution in China. In recent years, advances in real-time PM chemical characterization have created a new paradigm for PM studies in China. In this review, we summarize those advances, focusing on the most widely used mass spectrometric and ion chromatographic techniques. We describe the findings from those studies in terms of spatiotemporal variabilities, degree of neutralization and oxygenation, source apportionment, secondary formation, as well as collocated measurements of the chemical and physical (hygroscopic and optical) properties of PM. We also highlight the new insights gained from those findings and suggest future directions for further advancing our understanding of PM pollution in China via real-time chemical characterization.

  16. Development and new applications of quantum chemical simulation methodology

    International Nuclear Information System (INIS)

    Weiss, A. K. H.

    2012-01-01

    The Division of Theoretical Chemistry at the University of Innsbruck is focused on the study of chemical compounds in aqueous solution, in terms of mainly hybrid quantum mechanical / molecular mechanical molecular dynamics simulations (QM/MM MD). Besides the standard means of data analysis employed for such simulations, this study presents several advanced and capable algorithms for the description of structural and dynamic properties of the simulated species and its hydration. The first part of this thesis further presents selected exemplary simulations, in particular a comparative study of Formamide and N-methylformamide, Guanidinium, and Urea. An included review article further summarizes the major advances of these studies. The computer programs developed in the course of this thesis are by now well established in the research field. The second part of this study presents the theory and a development guide for a quantum chemical program, QuMuLuS, that is by now used as a QM program for recent QM/MM simulations at the division. In its course, this part presents newly developed algorithms for electron integral evaluation and point charge embedding. This program is validated in terms of benchmark computations. The associated theory is presented on a detailed level, to serve as a source for contemporary and future studies in the division. In the third and final part, further investigations of related topics are addressed. This covers additional schemes of molecular simulation analysis, new software, as well as a mathematical investigation of a non-standard two-electron integral. (author)

  17. A Collaborative Study of Disproportionate Chemical Risks in Seven Delaware Communities

    Science.gov (United States)

    Dryden, O.; Goldman, G. T.; White, R.; Moore, D.; Roberts, M.; Thomas, J.; Johnson, C.

    2017-12-01

    Studies have found that, compared to national averages, a significantly greater percentage of Blacks (African-Americans), Latinos (Hispanics), and people at or near poverty levels tend to live near industrial facilities that use large quantities of toxic chemicals and present a risk of major chemical disasters with potentially severe consequences for nearby communities. The Union of Concerned Scientists, the Environmental Justice Health Alliance for Chemical Policy Reform, and Delaware Concerned Residents for Environmental Justice collaborated on a study to examine the potential for cumulative impacts from health and safety risks for seven Delaware communities with a percentage of people of color and/or poverty levels greater than the Delaware average located along an industrial corridor in the northern portion of Delaware's New Castle County. These risks include close proximity to major industrial sources, as well as facilities that use large quantities of toxic, flammable or explosive chemicals and pose a high risk of a major chemical release or catastrophic incident. Additionally, proximity to contaminated waste sites was assessed, as well as the risk of cancer and potential for respiratory disease impacts from exposure to toxic air pollution. We found that people in these seven communities face a substantial cumulative health risk from exposure to toxic air pollution, proximity to polluting industrial facilities and hazardous chemical facilities, as well as contaminated waste sites. These health risks are substantially greater when compared to a wealthier and predominantly White Delaware community and for Delaware as a whole. Significant and expedited improvements in regulatory and public policy are needed at the national, state, and municipal levels to address the health and well-being of at-risk communities in Delaware and elsewhere.

  18. Surface variations affecting human dental enamel studied using nanomechanical and chemical analysis

    Science.gov (United States)

    Dickinson, Michelle Emma

    The enamel surface is the interface between the tooth and its ever changing oral environment. Cavity (caries) formation and extrinsic tooth staining are due, respectively, to degradation of the enamel structure under low pH conditions and interactions between salivary pellicle and dietary elements. Both of these occur at the enamel surface and are caused by the local environment changing the chemistry of the surface. The results can be detrimental to the enamel's mechanical integrity and aesthetics. Incipient carious lesions are the precursor to caries and form due to demineralisation of enamel. These carious lesions are a reversible structure where ions (e.g. Ca2+, F -) can diffuse in (remineralisation) to preserve the tooth's structural integrity. This investigation used controlled in vitro demineralisation and remineralisation to study artificial carious lesion formation and repair. The carious lesions were cross-sectioned and characterised using nanoindentation, electron probe micro-analysis and time of flight secondary ion mass spectrometry. Mechanical and chemical maps showed the carious lesion had a significantly reduced hardness and elastic modulus, and the calcium and phosphate content was lower than in sound enamel. Fluoride based remineralisation treatments gave a new phase (possibly fluorohydroxyapatite) within the lesion with mechanical properties higher than sound enamel. The acquired salivary pellicle is a protein-rich film formed by the physisorption of organic molecules in saliva onto the enamel surface. Its functions include lubrication during mastication and chemical protection. However, pellicle proteins react with dietary elements such as polyphenols (tannins in tea) causing a brown stain. This study has used in vitro dynamic nanoindentation and atomic force microscopy to examine normal and stained pellicles formed in vivo. The effects of polyphenols on the pellicle's mechanical properties and morphology have been studied. It was found that the

  19. Experimental study of chemical embolus therapy combined with radiotherapy for VX2 bone tumors

    International Nuclear Information System (INIS)

    Yamaguchi, Hiroshi; Mochizuki, Kazuo; Ishii, Yoshiaki

    2000-01-01

    We conducted an experimental study, using a combination of coarse crystal cisplatin and radiotherapy for bone tumors, to evaluate the possibility of the clinical application of chemical embolus therapy in the field of orthopedic surgery. Experimental femoral bone tumors were produced, in rabbits, using VX2 carcinoma. The rabbits were allocated to five groups: untreated control, embolus, chemical embolus, irradiation alone, and chemical embolus and irradiation combination. These therapies were evaluated comparatively, in terms of local antitumor effects (including body weight, X-ray findings, angiography, and histopathology) and in terms of inhibition of pulmonary metastasis. Local antitumor effects, as evaluated by all parameters, except for body weight, were significantly greater for the chemical and irradiation combination group than for the chemical embolus, irradiation alone, untreated control, and embolus groups. There was no significant difference in the inhibition of pulmonary metastasis among the chemical embolus and irradiation combination, chemical embolus, and irradiation alone groups. These findings demonstrated the synergistic effect of the combination of chemical embolus therapy and radiotherapy. In this study, however, no significant difference was found between the chemical embolus therapy alone and the combination therapy groups in the inhibitory effect on pulmonary tumor metastasis, suggesting the need to conduct combination therapy repeatedly in the clinical setting. (author)

  20. The direct measurement of the heteronuclear chemical shifts relative to tetramethylsilane

    International Nuclear Information System (INIS)

    Moritz, A.G.

    1988-12-01

    The measurement of heteronuclear chemical shifts using absolute frequencies of the heteronucleus and the 1 H resonance of tetramethylsilane has been examined. This method avoids the problems associated with external standards and gives results which can be obtained quickly and with high precision. The method has a number of advantages in the accurate measurement of chemical shifts, as for example 31 P in chemical warfare agents and related chemicals and allows multinuclear data to be obtained without dynamic range or potential interference problems. 15 refs., 4 tabs

  1. Comparative Studies of Physico-chemical Properties of Some ...

    African Journals Online (AJOL)

    The aim of this study was to evaluate some physico-chemical properties of four major general purpose cement (As, Br, De and Sk) sold in Nigerian market using standard methods; due to the persistent collapse of buildings. The results showed that Br cement recorded the least CaO content (56.17%) while De cement had ...

  2. Antiparallel Dynamic Covalent Chemistries

    NARCIS (Netherlands)

    Matysiak, Bartosz M.; Nowak, Piotr; Cvrtila, Ivica; Pappas, Charalampos G.; Liu, Bin; Komaromy, David; Otto, Sijbren

    2017-01-01

    The ability to design reaction networks with high, but addressable complexity is a necessary prerequisite to make advanced functional chemical systems. Dynamic combinatorial chemistry has, proven to be a useful tool in achieving complexity, however with some limitations in controlling it. Herein we

  3. Comparative sensitivity of human and rat neural cultures to chemical-induced inhibition of neurite outgrowth

    Energy Technology Data Exchange (ETDEWEB)

    Harrill, Joshua A.; Freudenrich, Theresa M.; Robinette, Brian L.; Mundy, William R., E-mail: mundy.william@epa.gov

    2011-11-15

    There is a need for rapid, efficient and cost-effective alternatives to traditional in vivo developmental neurotoxicity testing. In vitro cell culture models can recapitulate many of the key cellular processes of nervous system development, including neurite outgrowth, and may be used as screening tools to identify potential developmental neurotoxicants. The present study compared primary rat cortical cultures and human embryonic stem cell-derived neural cultures in terms of: 1) reproducibility of high content image analysis based neurite outgrowth measurements, 2) dynamic range of neurite outgrowth measurements and 3) sensitivity to chemicals which have been shown to inhibit neurite outgrowth. There was a large increase in neurite outgrowth between 2 and 24 h in both rat and human cultures. Image analysis data collected across multiple cultures demonstrated that neurite outgrowth measurements in rat cortical cultures were more reproducible and had higher dynamic range as compared to human neural cultures. Human neural cultures were more sensitive than rat cortical cultures to chemicals previously shown to inhibit neurite outgrowth. Parallel analysis of morphological (neurite count, neurite length) and cytotoxicity (neurons per field) measurements were used to detect selective effects on neurite outgrowth. All chemicals which inhibited neurite outgrowth in rat cortical cultures did so at concentrations which did not concurrently affect the number of neurons per field, indicating selective effects on neurite outgrowth. In contrast, more than half the chemicals which inhibited neurite outgrowth in human neural cultures did so at concentrations which concurrently decreased the number of neurons per field, indicating that effects on neurite outgrowth were secondary to cytotoxicity. Overall, these data demonstrate that the culture models performed differently in terms of reproducibility, dynamic range and sensitivity to neurite outgrowth inhibitors. While human neural

  4. Comparative sensitivity of human and rat neural cultures to chemical-induced inhibition of neurite outgrowth

    International Nuclear Information System (INIS)

    Harrill, Joshua A.; Freudenrich, Theresa M.; Robinette, Brian L.; Mundy, William R.

    2011-01-01

    There is a need for rapid, efficient and cost-effective alternatives to traditional in vivo developmental neurotoxicity testing. In vitro cell culture models can recapitulate many of the key cellular processes of nervous system development, including neurite outgrowth, and may be used as screening tools to identify potential developmental neurotoxicants. The present study compared primary rat cortical cultures and human embryonic stem cell-derived neural cultures in terms of: 1) reproducibility of high content image analysis based neurite outgrowth measurements, 2) dynamic range of neurite outgrowth measurements and 3) sensitivity to chemicals which have been shown to inhibit neurite outgrowth. There was a large increase in neurite outgrowth between 2 and 24 h in both rat and human cultures. Image analysis data collected across multiple cultures demonstrated that neurite outgrowth measurements in rat cortical cultures were more reproducible and had higher dynamic range as compared to human neural cultures. Human neural cultures were more sensitive than rat cortical cultures to chemicals previously shown to inhibit neurite outgrowth. Parallel analysis of morphological (neurite count, neurite length) and cytotoxicity (neurons per field) measurements were used to detect selective effects on neurite outgrowth. All chemicals which inhibited neurite outgrowth in rat cortical cultures did so at concentrations which did not concurrently affect the number of neurons per field, indicating selective effects on neurite outgrowth. In contrast, more than half the chemicals which inhibited neurite outgrowth in human neural cultures did so at concentrations which concurrently decreased the number of neurons per field, indicating that effects on neurite outgrowth were secondary to cytotoxicity. Overall, these data demonstrate that the culture models performed differently in terms of reproducibility, dynamic range and sensitivity to neurite outgrowth inhibitors. While human neural

  5. Wild canelas from the Brazilian Northeast: botanical, chemical and pharmocological studies

    International Nuclear Information System (INIS)

    Fernandes, A.A.; Alencar, J.W. de; Matos, F.J.A.; Craveiro, A.A.; Andrade, C.H.S.; Fonteles, M.C.; Viana, G.S.B.; Capelo, L.R.; Matos, F.F.

    Botanical, chemical and pharmacological studies were carried out with several types of the species Croton aff. zehntneri, called 'canelas ' at the Brazilian Northeastern region. Chemical studies showed that t-anetole, estragole, and sometimes eugenole are the most common components of the essential oils of these 'canelas'. The pharmacological studies were carried out with hidroalcoholic extract, essential oil and its aqueous phase obtained during the extraction process, by means of biological assays with various laboratory animals. Results of these tests are discussed. Emphasis is given on the possibility that some of the observed effects are due to the presence of anethole and estragole in the different types of the species studied. (M.A.) [pt

  6. Chemical Dynamics Studies of Reactions in Solids

    National Research Council Canada - National Science Library

    Thompson, Donald O

    1998-01-01

    ... the properties inherent in high-energy high-density materials. This research lays the groundwork for that by providing the theoretical and computational methods as well as accurate molecular and crystal models for important types of energetic systems...

  7. Exploring process dynamics by near infrared spectroscopy in lactic fermentations

    DEFF Research Database (Denmark)

    Svendsen, Carina; Cieplak, Tomasz; van der Berg, Franciscus Winfried J

    2016-01-01

    In the industrial production of yoghurt, measurement of pH is normally the only in-line technique applied as a real-time monitoring signalfor following the dynamics during the fermentation process. However, every dairy company would benefit from an in-line technique giving information about...... the chemical composition, physical/textural properties and/or microbial contamination. In this study lactic fermentation batches with the starter bacteria Streptococcus thermophilus and Lactobacillus delbrueckii subsp. bulgaricus are explored by in-line near infrared (NIR) spectroscopy. The dynamics obtained...

  8. Dynamic root uptake model for neutral lipophilic organics

    DEFF Research Database (Denmark)

    Trapp, Stefan

    2002-01-01

    and output to stem with the transpiration stream plus first-order metabolism and dilution by exponential growth. For chemicals with low or intermediate lipophilicity (log Kow , 2), there was no relevant difference between dynamic model and equilibrium approach. For lipophilic compounds, the dynamic model...

  9. A microfluidic flow-cell for the study of the ultrafast dynamics of biological systems

    Energy Technology Data Exchange (ETDEWEB)

    Chauvet, Adrien, E-mail: adrien.chauvet@epfl.ch; Chergui, Majed [Ecole Polytechnique Fédérale de Lausanne (EPFL), Laboratoire de Spectroscopie Ultrarapide, ISIC, Faculté des Sciences de Base, Station 6, 1015 Lausanne (Switzerland); Tibiletti, Tania; Caffarri, Stefano [Aix Marseille Université, CNRS, CEA, UMR 7265 Biologie Végétale et Microbiologie Environnementales, 13009 Marseille (France)

    2014-10-01

    The study of biochemical dynamics by ultrafast spectroscopic methods is often restricted by the limited amount of liquid sample available, while the high repetition rate of light sources can induce photodamage. In order to overcome these limitations, we designed a high flux, sub-ml, capillary flow-cell. While the 0.1 mm thin window of the 0.5 mm cross-section capillary ensures an optimal temporal resolution and a steady beam deviation, the cell-pump generates flows up to ~0.35 ml/s that are suitable to pump laser repetition rates up to ~14 kHz, assuming a focal spot-diameter of 100 μm. In addition, a decantation chamber efficiently removes bubbles and allows, via septum, for the addition of chemicals while preserving the closed atmosphere. The minimal useable amount of sample is ~250 μl.

  10. Using chemical imaging to study bonding of dissimilar alloys

    International Nuclear Information System (INIS)

    Wuhrer, R.; Phillips, M.R.; Huggett, P.

    2002-01-01

    Full text: New welding techniques are currently being developed to bond very dissimilar materials such as cast irons or wear resistant steels welded to mild steel. X-ray mapping and chemical phase imaging provides useful information on the mass transport across the interface as well as phase segregation within the weld joint. Cast iron / steel and wear resistant steel / mild steel weld joints were mounted in a bakelite mount, cross-sectioned with a diamond wafering blade and polished to an optical finish using diamond abrasives. X-ray maps were collected at over a range of accelerating voltages using a Moran Scientific energy dispersive x-ray analysis and mapping system. These elemental x-ray maps were used to generate scatter plots, where pixel frequency versus element concentration profiles are plotted against each other in two or three dimensions for selected elements within the sample. The clusters observed in these plots correspond to different phases within the weld seam. The contributing pixels to each cluster can be used to reconstruct the spatial distribution of its associated phase in a chemical image of the specimen. Of particular interest to this study were the branches and links between clusters in each scatter plot and how these features correlate the chemical distribution of elements both in and around the bond region. Preliminary analysis indicated that these links and branches in the scatter plot correspond to solid solutions between chemical phases and diffusion gradients. Proper interpretation of these scatter plots will provide a better understanding of the chemical processes involved in welding dissimilar materials. Copyright (2002) Australian Society for Electron Microscopy Inc

  11. Development of High Temperature/High Sensitivity Novel Chemical Resistive Sensor

    Energy Technology Data Exchange (ETDEWEB)

    Ma, Chunrui [Univ. of Texas, San Antonio, TX (United States); Enriquez, Erik [Univ. of Texas, San Antonio, TX (United States); Wang, Haibing [Univ. of Texas, San Antonio, TX (United States); Xu, Xing [Univ. of Texas, San Antonio, TX (United States); Bao, Shangyong [Univ. of Texas, San Antonio, TX (United States); Collins, Gregory [Univ. of Texas, San Antonio, TX (United States)

    2013-08-13

    The research has been focused to design, fabricate, and develop high temperature/high sensitivity novel multifunctional chemical sensors for the selective detection of fossil energy gases used in power and fuel systems. By systematically studying the physical properties of the LnBaCo2O5+d (LBCO) [Ln=Pr or La] thin-films, a new concept chemical sensor based high temperature chemical resistant change has been developed for the application for the next generation highly efficient and near zero emission power generation technologies. We also discovered that the superfast chemical dynamic behavior and an ultrafast surface exchange kinetics in the highly epitaxial LBCO thin films. Furthermore, our research indicates that hydrogen can superfast diffuse in the ordered oxygen vacancy structures in the highly epitaxial LBCO thin films, which suggest that the LBCO thin film not only can be an excellent candidate for the fabrication of high temperature ultra sensitive chemical sensors and control systems for power and fuel monitoring systems, but also can be an excellent candidate for the low temperature solid oxide fuel cell anode and cathode materials.

  12. Study of novel mechano-chemical activation process of red mud to optimize nitrate removal from water.

    Science.gov (United States)

    Alighardashi, A; Gharibi, H R; Raygan, Sh; Akbarzadeh, A

    2016-01-01

    Red mud (RM) is the industrial waste of alumina production and causes serious environmental risks. In this paper, a novel activation procedure for RM (mechano-chemical processing) is proposed in order to improve the nitrate adsorption from water. High-energy milling and acidification were selected as mechanical and chemical activation methods, respectively. Synthesized samples of adsorbent were produced considering two parameters of activation: acid concentrations and acidification time in two selected milling times. Optimization of the activation process was based on nitrate removal from a stock solution. Experimental data were analyzed with two-way analysis of variance and Kruskal-Wallis methods to verify and discover the accuracy and probable errors. Best conditions (acceptable removal percentage > 75) were 17.6% w/w for acid concentrate and 19.9 minutes for acidification time in 8 hours for milling time. A direct relationship between increase in nitrate removal and increasing the acid concentration and acidification time was observed. The adsorption isotherms were studied and compared with other nitrate adsorbents. Characterization tests (X-ray fluorescence, X-ray diffraction, Fourier transform infrared spectrophotometry, dynamic light scattering, surface area analysis and scanning electron microscopy) were conducted for both raw and activated adsorbents. Results showed noticeable superiority in characteristics after activation: higher specific area and porosity, lower particle size and lower agglomeration in structure.

  13. Dynamics of polymers in a good solvent - a molecular dynamics study using the Connection Machine

    International Nuclear Information System (INIS)

    Shannon, S.R.; Choy, T.C.

    1996-01-01

    In recent times the use of molecular dynamics simulations has become an important tool in modelling and understanding the dynamics of interacting many-body systems. With recent advances in computing power it is now feasible to perform modelling of systems which contain a large number of interacting particles, and thus to simulate the behaviour of real systems reasonably. Our earlier discoveries of anomalous corrections to scaling behaviour of the Edward's polymer were applied to study the dynamical behaviour of two dimensional polymer systems - either a single chain immersed in a fluid, a pure polymer melt, or with any concentration of polymers in the fluid. By choosing a suitable interaction potential between the fluid particles and the monomers, we are able to study the experimentally observable time dependent structure factor of polymers in a good solvent. Simulations were performed using the Connection Machine CM5 supercomputer at the Australian National University which due to its fast multi- processor nearest neighbour communications facility, enables us to easily model large systems of at least 3000 fluid plus monomer particles. Our study is based on a finite difference solution of Newton's equations of motion i.e. the Verlet algorithm, and the results are used to test current theories of polymer dynamics, which were based primarily on the earlier models proposed by Rouse (1953) and Zimm (1956). In particular dynamical scaling predictions is scrutinised to examine the effects due to the anomalous corrections-to-scaling behaviour found in an earlier work using finite-size scaling analysis of Monte-Carlo data and now understood via a new perturbation concept

  14. An agar gel membrane-PDMS hybrid microfluidic device for long term single cell dynamic study.

    Science.gov (United States)

    Wong, Ieong; Atsumi, Shota; Huang, Wei-Chih; Wu, Tung-Yun; Hanai, Taizo; Lam, Miu-Ling; Tang, Ping; Yang, Jian; Liao, James C; Ho, Chih-Ming

    2010-10-21

    Significance of single cell measurements stems from the substantial temporal fluctuations and cell-cell variability possessed by individual cells. A major difficulty in monitoring surface non-adherent cells such as bacteria and yeast is that these cells tend to aggregate into clumps during growth, obstructing the tracking or identification of single-cells over long time periods. Here, we developed a microfluidic platform for long term single-cell tracking and cultivation with continuous media refreshing and dynamic chemical perturbation capability. The design highlights a simple device-assembly process between PDMS microchannel and agar membrane through conformal contact, and can be easily adapted by microbiologists for their routine laboratory use. The device confines cell growth in monolayer between an agar membrane and a glass surface. Efficient nutrient diffusion through the membrane and reliable temperature maintenance provide optimal growth condition for the cells, which exhibited fast exponential growth and constant distribution of cell sizes. More than 24 h of single-cell tracking was demonstrated on a transcription-metabolism integrated synthetic biological model, the gene-metabolic oscillator. Single cell morphology study under alcohol toxicity allowed us to discover and characterize cell filamentation exhibited by different E. coli isobutanol tolerant strains. We believe this novel device will bring new capabilities to quantitative microbiology, providing a versatile platform for single cell dynamic studies.

  15. Supramolecular assembly/reassembly processes: molecular motors and dynamers operating at surfaces.

    Science.gov (United States)

    Ciesielski, Artur; Samorì, Paolo

    2011-04-01

    Among the many significant advances within the field of supramolecular chemistry over the past decades, the development of the so-called "dynamers" features a direct relevance to materials science. Defined as "combinatorial dynamic polymers", dynamers are constitutional dynamic systems and materials resulting from the application of the principles of supramolecular chemistry to polymer science. Like supramolecular materials in general, dynamers are reversible dynamic multifunctional architectures, capable of modifying their constitution by exchanging, recombining, incorporating components. They may exhibit a variety of novel properties and behave as adaptive materials. In this review we focus on the design of responsive switchable monolayers, i.e. monolayers capable to undergo significant changes in their physical or chemical properties as a result of external stimuli. Scanning tunneling microscopy studies provide direct evidence with a sub-nanometre resolution, on the formation and dynamic response of these self-assembled systems featuring controlled geometries and properties.

  16. Feedback coupling in dynamical systems

    Science.gov (United States)

    Trimper, Steffen; Zabrocki, Knud

    2003-05-01

    Different evolution models are considered with feedback-couplings. In particular, we study the Lotka-Volterra system under the influence of a cumulative term, the Ginzburg-Landau model with a convolution memory term and chemical rate equations with time delay. The memory leads to a modified dynamical behavior. In case of a positive coupling the generalized Lotka-Volterra system exhibits a maximum gain achieved after a finite time, but the population will die out in the long time limit. In the opposite case, the time evolution is terminated in a crash. Due to the nonlinear feedback coupling the two branches of a bistable model are controlled by the the strength and the sign of the memory. For a negative coupling the system is able to switch over between both branches of the stationary solution. The dynamics of the system is further controlled by the initial condition. The diffusion-limited reaction is likewise studied in case the reacting entities are not available simultaneously. Whereas for an external feedback the dynamics is altered, but the stationary solution remain unchanged, a self-organized internal feedback leads to a time persistent solution.

  17. Dynamic MRI study for breast tumors

    International Nuclear Information System (INIS)

    Seki, Tsuneaki

    1990-01-01

    Application of MRI for diagnosis of breast tumors was retrospectively examined in 103 consecutive cases. Contrast enhancement, mostly by dynamic study, was performed in 83 cases using Gd-DTPA and 0.5 T superconductive apparatus. Results were compared to those of mammography and sonography. On dynamic study, carcinoma showed abrupt rise of signal intensity with clear-cut peak formation in early phase, while benign fibroadenoma showed slow rise of signal intensity and prolonged enhancement without peak formation. In 12 of 33 carcinomas (33%), peripheral ring enhancement was noted reflecting vascular stroma of histologic sections. All fibroadenomas showed homogenous enhancement without peripheral ring. In MRI, sensitivity, specificity, and accuracy were 86%, 96%, 91%. In mammography 82%, 95%, 87% and in ultrasonography 91%, 95%, 93%. Although MRI should not be regarded as routine diagnostic procedure because of expense and limited availability, it may afford useful additional information when standard mammographic findings are not conclusive. (author)

  18. Bandwidth Study on Energy Use and Potential Energy Saving Opportunities in U.S. Chemical Manufacturing

    Energy Technology Data Exchange (ETDEWEB)

    Sabine Brueske, Caroline Kramer, Aaron Fisher

    2015-06-01

    Energy bandwidth studies of U.S. manufacturing sectors can serve as foundational references in framing the range (or bandwidth) of potential energy savings opportunities. This bandwidth study examines energy consumption and potential energy savings opportunities in U.S. chemical manufacturing. The study relies on multiple sources to estimate the energy used in the production of 74 individual chemicals, representing 57% of sector-wide energy consumption. Energy savings opportunities for individual chemicals and for 15 subsectors of chemicals manufacturing are based on technologies currently in use or under development; these potential savings are then extrapolated to estimate sector-wide energy savings opportunity.

  19. All-in-one light-tunable borated phosphors with chemical and luminescence dynamical control resolution.

    Science.gov (United States)

    Lin, Chun Che; Liu, Yun-Ping; Xiao, Zhi Ren; Wang, Yin-Kuo; Cheng, Bing-Ming; Liu, Ru-Shi

    2014-06-25

    Single-composition white-emitting phosphors with superior intrinsic properties upon excitation by ultraviolet light-emitting diodes are important constituents of next-generation light sources. Borate-based phosphors, such as NaSrBO3:Ce(3+) and NaCaBO3:Ce(3+), have stronger absorptions in the near-ultraviolet region as well as better chemical/physical stability than oxides. Energy transfer effects from sensitizer to activator caused by rare-earth ions are mainly found in the obtained photoluminescence spectra and lifetime. The interactive mechanisms of multiple dopants are ambiguous in most cases. We adjust the doping concentration in NaSrBO3:RE (RE = Ce(3+), Tb(3+), Mn(2+)) to study the energy transfer effects of Ce(3+) to Tb(3+) and Mn(2+) by comparing the experimental data and theoretical calculation. The vacuum-ultraviolet experimental determination of the electronic energy levels for Ce(3+) and Tb(3+) in the borate host regarding the 4f-5d and 4f-4f configurations are described. Evaluation of the Ce(3+)/Mn(2+) intensity ratios as a function of Mn(2+) concentration is based on the analysis of the luminescence dynamical process and fluorescence lifetime measurements. The results closely agree with those directly obtained from the emission spectra. Density functional calculations are performed using the generalized gradient approximation plus an on-site Coulombic interaction correction scheme to investigate the forbidden mechanism of interatomic energy transfer between the NaSrBO3:Ce(3+) and NaSrBO3:Eu(2+) systems. Results indicate that the NaSrBO3:Ce(3+), Tb(3+), and Mn(2+) phosphors can be used as a novel white-emitting component of UV radiation-excited devices.

  20. Proceedings of 20. Symposium of Malaysian Chemical Engineers (SOMChE 2006)

    International Nuclear Information System (INIS)

    2006-12-01

    The objective of the symposium is to provide a platform for participants and relevant chemical engineering community to meet and encourage expertise and knowledge sharing and to allow recent chemical engineering research and innovation works to be properly documented, displayed and made known to interested parties. The subjects discussed are advanced material modeling and simulation bioprocess, catalysis, chemical engineering education (outcome-based education), computational fluid dynamics, drying technology, energy, environment, fine chemicals, food engineering, oil and gas, oleochemical, particle technology, petrochemical, pharmaceutical engineering, polymer technology, process control, process system, engineering, reaction engineering, renewable energy, separation