WorldWideScience

Sample records for chemical reactivity

  1. Steam-chemical reactivity for irradiated beryllium

    Energy Technology Data Exchange (ETDEWEB)

    Anderl, R.A.; McCarthy, K.A.; Oates, M.A.; Petti, D.A.; Pawelko, R.J.; Smolik, G.R. [Idaho National Engineering and Environmental Lab., Idaho Falls, ID (United States)

    1998-01-01

    This paper reports the results of an experimental investigation to determine the influence of neutron irradiation effects and annealing on the chemical reactivity of beryllium exposed to steam. The work entailed measurements of the H{sub 2} generation rates for unirradiated and irradiated Be and for irradiated Be that had been previously annealed at different temperatures ranging from 450degC to 1200degC. H{sub 2} generation rates were similar for irradiated and unirradiated Be in steam-chemical reactivity experiments at temperatures between 450degC and 600degC. For irradiated Be exposed to steam at 700degC, the chemical reactivity accelerated rapidly and the specimen experienced a temperature excursion. Enhanced chemical reactivity at temperatures between 400degC and 600degC was observed for irradiated Be annealed at temperatures of 700degC and higher. This reactivity enhancement could be accounted for by the increased specific surface area resulting from development of a surface-connected porosity in the irradiated-annealed Be. (author)

  2. Chemical Reactivity Test (CRT)

    Energy Technology Data Exchange (ETDEWEB)

    Zaka, F. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

    2016-12-13

    The Chemical Reactivity Test (CRT) is used to determine the thermal stability of High Explosives (HEs) and chemical compatibility between (HEs) and alien materials. The CRT is one of the small-scale safety tests performed on HE at the High Explosives Applications Facility (HEAF).

  3. An autonomous organic reaction search engine for chemical reactivity

    Science.gov (United States)

    Dragone, Vincenza; Sans, Victor; Henson, Alon B.; Granda, Jaroslaw M.; Cronin, Leroy

    2017-06-01

    The exploration of chemical space for new reactivity, reactions and molecules is limited by the need for separate work-up-separation steps searching for molecules rather than reactivity. Herein we present a system that can autonomously evaluate chemical reactivity within a network of 64 possible reaction combinations and aims for new reactivity, rather than a predefined set of targets. The robotic system combines chemical handling, in-line spectroscopy and real-time feedback and analysis with an algorithm that is able to distinguish and select the most reactive pathways, generating a reaction selection index (RSI) without need for separate work-up or purification steps. This allows the automatic navigation of a chemical network, leading to previously unreported molecules while needing only to do a fraction of the total possible reactions without any prior knowledge of the chemistry. We show the RSI correlates with reactivity and is able to search chemical space using the most reactive pathways.

  4. Reactive chemicals and process hazards

    International Nuclear Information System (INIS)

    Surianarayanan, M.

    2016-01-01

    Exothermic chemical reactions are often accompanied by significant heat release, and therefore, need a thorough investigation before they are taken to a plant scale. Sudden thermal energy releases from exothermic decompositions and runaway reactions have contributed to serious fire and explosions in several chemical process plants. Similarly, thermal runaway had also occurred in storage and transportation of reactive chemicals. The secondary events of thermal runaway reactions can be rupture of process vessel, toxic spills and release of explosive vapor clouds or combination of these also. The explosion hazards are governed by the system thermodynamics and kinetics of the thermal process. Theoretical prediction of limiting temperature is difficult due to process complexities. Further, the kinetic data obtained through classical techniques, at conditions far away from runaway situation, is often not valid for assessing the runaway behavior of exothermic processes. The main focus of this lecture is to discuss the causes and several contributing factors for thermal runaway and instability and present analyses of the methodologies of the new instrumental techniques for assessing the thermal hazards of reactive chemicals during processing, storage and transportation. (author)

  5. Chemical reactivity of cation-exchanged zeolites

    OpenAIRE

    Pidko, E.A.

    2008-01-01

    Zeolites modified with metal cations have been extensively studied during the last two decades because of their wide application in different technologically important fields such as catalysis, adsorption and gas separation. Contrary to the well-understood mechanisms of chemical reactions catalyzed by Brønsted acid sites in the hydrogen forms of zeolites, the nature of chemical reactivity, and related, the structure of the metal-containing ions in cation-exchanged zeolites remains the subject...

  6. Modeling food matrix effects on chemical reactivity: Challenges and perspectives.

    Science.gov (United States)

    Capuano, Edoardo; Oliviero, Teresa; van Boekel, Martinus A J S

    2017-06-29

    The same chemical reaction may be different in terms of its position of the equilibrium (i.e., thermodynamics) and its kinetics when studied in different foods. The diversity in the chemical composition of food and in its structural organization at macro-, meso-, and microscopic levels, that is, the food matrix, is responsible for this difference. In this viewpoint paper, the multiple, and interconnected ways the food matrix can affect chemical reactivity are summarized. Moreover, mechanistic and empirical approaches to explain and predict the effect of food matrix on chemical reactivity are described. Mechanistic models aim to quantify the effect of food matrix based on a detailed understanding of the chemical and physical phenomena occurring in food. Their applicability is limited at the moment to very simple food systems. Empirical modeling based on machine learning combined with data-mining techniques may represent an alternative, useful option to predict the effect of the food matrix on chemical reactivity and to identify chemical and physical properties to be further tested. In such a way the mechanistic understanding of the effect of the food matrix on chemical reactions can be improved.

  7. 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)

  8. Phase rule calculations and the thermodynamics of reactive systems under chemical equilibrium

    Directory of Open Access Journals (Sweden)

    PLATT G. M.

    1999-01-01

    Full Text Available In this paper, we examine the resolution of some phase rule problems within the context of multiple chemical equilibrium reactions, using cubic equations of state and an activity coefficient model. Bubble and dew reactive surfaces, reactive azeotropic loci and reactive critical loci are generated and presented in graphical form. Also isobaric bubble and dew reactive enthalpy loci, which may be useful in the modeling of reactive distillation operations, are depicted. All the formalism here employed is developed within the coordinate transformation of Ung and Doherty, which is appropriate for equilibrium reactive or multireactive systems. The major contribution of this work is the determination of critical loci for reactive or multireactive equilibrium systems. Since it is known that for some class of chemical reactions the kinetics and product distribution exhibit high sensitivity to pressure near criticality, the present study may be useful as a predicting tool in these cases if the chemical equilibrium condition is not too far from the real phenomenon.

  9. Reactivity of Dual-Use Decontaminants with Chemical Warfare Agents

    Science.gov (United States)

    2016-07-01

    REACTIVITY OF DUAL-USE DECONTAMINANTS WITH CHEMICAL WARFARE AGENTS ECBC-TR-1384... Decontaminants with Chemical Warfare Agents 5a. CONTRACT NUMBER 5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER 6. AUTHOR(S) Willis, Matthew P...extraction) of chemical warfare agents from materials. 15. SUBJECT TERMS GD HD Decontamination Hazard mitigation VX Chemical warfare agent Liquid-phase

  10. Communication: Enhanced chemical reactivity of graphene on a Ni(111) substrate

    Energy Technology Data Exchange (ETDEWEB)

    Ambrosetti, Alberto; Silvestrelli, Pier Luigi [Dipartimento di Fisica e Astronomia, Università di Padova, via Marzolo 8, I–35131 Padova, Italy and DEMOCRITOS National Simulation Center of the Italian Istituto Officina dei Materiali (IOM) of the Italian National Research Council (CNR), Trieste (Italy)

    2016-03-21

    Due to the unique combination of structural, mechanical, and transport properties, graphene has emerged as an exceptional candidate for catalysis applications. The low chemical reactivity caused by sp{sup 2} hybridization and strongly delocalized π electrons, however, represents a main challenge for straightforward use of graphene in its pristine, free-standing form. Following recent experimental indications, we show that due to charge hybridization, a Ni(111) substrate can enhance the chemical reactivity of graphene, as exemplified by the interaction with the CO molecule. While CO only physisorbs on free-standing graphene, chemisorption of CO involving formation of ethylene dione complexes is predicted in Ni(111)-graphene. Higher chemical reactivity is also suggested in the case of oxidized graphene, opening the way to a simple and efficient control of graphene chemical properties, devoid of complex defect patterning or active metallic structures deposition.

  11. Communication: Enhanced chemical reactivity of graphene on a Ni(111) substrate

    International Nuclear Information System (INIS)

    Ambrosetti, Alberto; Silvestrelli, Pier Luigi

    2016-01-01

    Due to the unique combination of structural, mechanical, and transport properties, graphene has emerged as an exceptional candidate for catalysis applications. The low chemical reactivity caused by sp 2 hybridization and strongly delocalized π electrons, however, represents a main challenge for straightforward use of graphene in its pristine, free-standing form. Following recent experimental indications, we show that due to charge hybridization, a Ni(111) substrate can enhance the chemical reactivity of graphene, as exemplified by the interaction with the CO molecule. While CO only physisorbs on free-standing graphene, chemisorption of CO involving formation of ethylene dione complexes is predicted in Ni(111)-graphene. Higher chemical reactivity is also suggested in the case of oxidized graphene, opening the way to a simple and efficient control of graphene chemical properties, devoid of complex defect patterning or active metallic structures deposition.

  12. Revisiting the chemical reactivity indices as the state function derivatives. The role of classical chemical hardness

    Energy Technology Data Exchange (ETDEWEB)

    Malek, Ali; Balawender, Robert, E-mail: rbalawender@ichf.edu.pl [Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, PL-01-224 Warsaw (Poland)

    2015-02-07

    The chemical reactivity indices as the equilibrium state-function derivatives are revisited. They are obtained in terms of the central moments (fluctuation formulas). To analyze the role of the chemical hardness introduced by Pearson [J. Am. Chem. Soc. 105, 7512 (1983)], the relations between the derivatives up to the third-order and the central moments are obtained. As shown, the chemical hardness and the chemical potential are really the principal indices of the chemical reactivity theory. It is clear from the results presented here that the chemical hardness is not the derivative of the Mulliken chemical potential (this means also not the second derivative of the energy at zero-temperature limit). The conventional quadratic dependence of energy, observed at finite temperature, reduces to linear dependence on the electron number at zero-temperature limit. The chemical hardness plays a double role in the admixture of ionic states to the reference neutral state energy: it determines the amplitude of the admixture and regulates the damping of its thermal factor.

  13. Revisiting the chemical reactivity indices as the state function derivatives. The role of classical chemical hardness

    International Nuclear Information System (INIS)

    Malek, Ali; Balawender, Robert

    2015-01-01

    The chemical reactivity indices as the equilibrium state-function derivatives are revisited. They are obtained in terms of the central moments (fluctuation formulas). To analyze the role of the chemical hardness introduced by Pearson [J. Am. Chem. Soc. 105, 7512 (1983)], the relations between the derivatives up to the third-order and the central moments are obtained. As shown, the chemical hardness and the chemical potential are really the principal indices of the chemical reactivity theory. It is clear from the results presented here that the chemical hardness is not the derivative of the Mulliken chemical potential (this means also not the second derivative of the energy at zero-temperature limit). The conventional quadratic dependence of energy, observed at finite temperature, reduces to linear dependence on the electron number at zero-temperature limit. The chemical hardness plays a double role in the admixture of ionic states to the reference neutral state energy: it determines the amplitude of the admixture and regulates the damping of its thermal factor

  14. Fluxes of chemically reactive species inferred from mean concentration measurements

    NARCIS (Netherlands)

    Galmarini, S.; Vilà-Guerau De Arellano, J.; Duyzer, J.H.

    1997-01-01

    A method is presented for the calculation of the fluxes of chemically reactive species on the basis of routine measurements of meteorological variables and chemical species. The method takes explicity into account the influence of chemical reactions on the fluxes of the species. As a demonstration

  15. Chemical stability and in chemico reactivity of 24 fragrance ingredients of concern for skin sensitization risk assessment.

    Science.gov (United States)

    Avonto, Cristina; Wang, Mei; Chittiboyina, Amar G; Vukmanovic, Stanislav; Khan, Ikhlas A

    2018-02-01

    Twenty-four pure fragrance ingredients have been identified as potential concern for skin sensitization. Several of these compounds are chemically unstable and convert into reactive species upon exposure to air or light. In the present work, a systematic investigation of the correlation between chemical stability and reactivity has been undertaken. The compounds were subjected to forced photodegradation for three months and the chemical changes were studied with GC-MS. At the end of the stability study, two-thirds of the samples were found to be unstable. The generation of chemically reactive species was investigated using the in chemico HTS-DCYA assay. Eleven and fourteen compounds were chemically reactive before and after three months, respectively. A significant increase in reactivity upon degradation was found for isoeugenol, linalool, limonene, lyral, citronellol and geraniol; in the same conditions, the reactivity of hydroxycitronellal decreased. The non-reactive compounds α-isomethyl ionone, benzyl alcohol, amyl cinnamal and farnesol became reactive after photo-oxidative degradation. Overall, forced degradation resulted in four non-reactive fragrance compounds to display in chemico thiol reactivity, while ten out of 24 compounds remained inactive. Chemical degradation does not necessarily occur with generation of reactive species. Non-chemical activation may be involved for the 10 stable unreactive compounds. Copyright © 2017 Elsevier Ltd. All rights reserved.

  16. Chemical Reactivity as Described by Quantum Chemical Methods

    Directory of Open Access Journals (Sweden)

    F. De Proft

    2002-04-01

    Full Text Available Abstract: Density Functional Theory is situated within the evolution of Quantum Chemistry as a facilitator of computations and a provider of new, chemical insights. The importance of the latter branch of DFT, conceptual DFT is highlighted following Parr's dictum "to calculate a molecule is not to understand it". An overview is given of the most important reactivity descriptors and the principles they are couched in. Examples are given on the evolution of the structure-property-wave function triangle which can be considered as the central paradigm of molecular quantum chemistry to (for many purposes a structure-property-density triangle. Both kinetic as well as thermodynamic aspects can be included when further linking reactivity to the property vertex. In the field of organic chemistry, the ab initio calculation of functional group properties and their use in studies on acidity and basicity is discussed together with the use of DFT descriptors to study the kinetics of SN2 reactions and the regioselectivity in Diels Alder reactions. Similarity in reactivity is illustrated via a study on peptide isosteres. In the field of inorganic chemistry non empirical studies of adsorption of small molecules in zeolite cages are discussed providing Henry constants and separation constants, the latter in remarkable good agreement with experiments. Possible refinements in a conceptual DFT context are presented. Finally an example from biochemistry is discussed : the influence of point mutations on the catalytic activity of subtilisin.

  17. Rock fracture processes in chemically reactive environments

    Science.gov (United States)

    Eichhubl, P.

    2015-12-01

    Rock fracture is traditionally viewed as a brittle process involving damage nucleation and growth in a zone ahead of a larger fracture, resulting in fracture propagation once a threshold loading stress is exceeded. It is now increasingly recognized that coupled chemical-mechanical processes influence fracture growth in wide range of subsurface conditions that include igneous, metamorphic, and geothermal systems, and diagenetically reactive sedimentary systems with possible applications to hydrocarbon extraction and CO2 sequestration. Fracture processes aided or driven by chemical change can affect the onset of fracture, fracture shape and branching characteristics, and fracture network geometry, thus influencing mechanical strength and flow properties of rock systems. We are investigating two fundamental modes of chemical-mechanical interactions associated with fracture growth: 1. Fracture propagation may be aided by chemical dissolution or hydration reactions at the fracture tip allowing fracture propagation under subcritical stress loading conditions. We are evaluating effects of environmental conditions on critical (fracture toughness KIc) and subcritical (subcritical index) fracture properties using double torsion fracture mechanics tests on shale and sandstone. Depending on rock composition, the presence of reactive aqueous fluids can increase or decrease KIc and/or subcritical index. 2. Fracture may be concurrent with distributed dissolution-precipitation reactions in the hostrock beyond the immediate vicinity of the fracture tip. Reconstructing the fracture opening history recorded in crack-seal fracture cement of deeply buried sandstone we find that fracture length growth and fracture opening can be decoupled, with a phase of initial length growth followed by a phase of dominant fracture opening. This suggests that mechanical crack-tip failure processes, possibly aided by chemical crack-tip weakening, and distributed solution-precipitation creep in the

  18. Reactive solute transport in physically and chemically heterogeneous porous media with multimodal reactive mineral facies: the Lagrangian approach.

    Science.gov (United States)

    Soltanian, Mohamad Reza; Ritzi, Robert W; Dai, Zhenxue; Huang, Chao Cheng

    2015-03-01

    Physical and chemical heterogeneities have a large impact on reactive transport in porous media. Examples of heterogeneous attributes affecting reactive mass transport are the hydraulic conductivity (K), and the equilibrium sorption distribution coefficient (Kd). This paper uses the Deng et al. (2013) conceptual model for multimodal reactive mineral facies and a Lagrangian-based stochastic theory in order to analyze the reactive solute dispersion in three-dimensional anisotropic heterogeneous porous media with hierarchical organization of reactive minerals. An example based on real field data is used to illustrate the time evolution trends of reactive solute dispersion. The results show that the correlation between the hydraulic conductivity and the equilibrium sorption distribution coefficient does have a significant effect on reactive solute dispersion. The anisotropy ratio does not have a significant effect on reactive solute dispersion. Furthermore, through a sensitivity analysis we investigate the impact of changing the mean, variance, and integral scale of K and Kd on reactive solute dispersion. Copyright © 2014 Elsevier Ltd. All rights reserved.

  19. Local chemical potential, local hardness, and dual descriptors in temperature dependent chemical reactivity theory.

    Science.gov (United States)

    Franco-Pérez, Marco; Ayers, Paul W; Gázquez, José L; Vela, Alberto

    2017-05-31

    In this work we establish a new temperature dependent procedure within the grand canonical ensemble, to avoid the Dirac delta function exhibited by some of the second order chemical reactivity descriptors based on density functional theory, at a temperature of 0 K. Through the definition of a local chemical potential designed to integrate to the global temperature dependent electronic chemical potential, the local chemical hardness is expressed in terms of the derivative of this local chemical potential with respect to the average number of electrons. For the three-ground-states ensemble model, this local hardness contains a term that is equal to the one intuitively proposed by Meneses, Tiznado, Contreras and Fuentealba, which integrates to the global hardness given by the difference in the first ionization potential, I, and the electron affinity, A, at any temperature. However, in the present approach one finds an additional temperature-dependent term that introduces changes at the local level and integrates to zero. Additionally, a τ-hard dual descriptor and a τ-soft dual descriptor given in terms of the product of the global hardness and the global softness multiplied by the dual descriptor, respectively, are derived. Since all these reactivity indices are given by expressions composed of terms that correspond to products of the global properties multiplied by the electrophilic or nucleophilic Fukui functions, they may be useful for studying and comparing equivalent sites in different chemical environments.

  20. Local Chemical Reactivity of a Metal Alloy Surface

    DEFF Research Database (Denmark)

    Hammer, Bjørk; Scheffler, Matthias

    1995-01-01

    The chemical reactivity of a metal alloy surface is studied by density functional theory investigating the interaction of H2 with NiAl(110). The energy barrier for H2 dissociation is largely different over the Al and Ni sites without, however, reflecting the barriers over the single component metal...

  1. Chemical and physical characteristics of phosphate rock materials of varying reactivity

    International Nuclear Information System (INIS)

    Syers, J.K.; Currie, L.D.

    1986-01-01

    Several chemical and physical properties of 10 phosphate rock (PR) materials of varying reactivity were evaluated. The highest concentrations of As and Cd were noted. Because Cd and U can accumulate in biological systems, it may be necessary to direct more attention towards the likely implications of Cd and U concentrations when evaluating a PR for direct application. Three sequential extractions with 2% citric acid may be more useful for comparing the chemical solubility of PR materials, particularly for those containing appreciable CaC0 3 . The poor relationship obtained between surface area and the solubility of the PR materials suggests that surface area plays a secondary role to chemical reactivity in controlling the solubility of a PR in a chemical extractant. A Promesh plot provided an effective method for describing the particle-size characteristics of those PR materials which occurred as sands. Fundamental characteristics, such as mean particle size and uniformity, can readily be determined from a Promesh plot. (author)

  2. Importance of asparagine on the conformational stability and chemical reactivity of selected anti-inflammatory peptides

    Energy Technology Data Exchange (ETDEWEB)

    Soriano-Correa, Catalina, E-mail: csorico@comunidad.unam.mx [Química Computacional, Facultad de Estudios Superiores (FES)-Zaragoza, Universidad Nacional Autónoma de México (UNAM), Iztapalapa, C.P. 09230 México, D.F. (Mexico); Barrientos-Salcedo, Carolina [Laboratorio de Química Médica y Quimiogenómica, Facultad de Bioanálisis Campus Veracruz-Boca del Río, Universidad Veracruzana, C.P. 91700 Veracruz (Mexico); Campos-Fernández, Linda; Alvarado-Salazar, Andres [Química Computacional, Facultad de Estudios Superiores (FES)-Zaragoza, Universidad Nacional Autónoma de México (UNAM), Iztapalapa, C.P. 09230 México, D.F. (Mexico); Esquivel, Rodolfo O. [Departamento de Química, Universidad Autónoma Metropolitana-Iztapalapa (UAM-Iztapalapa), C.P. 09340 México, D.F. (Mexico)

    2015-08-18

    Highlights: • Asparagine plays an important role to anti-inflammatory effect of peptides. • The electron-donor substituent groups favor the formation of the hydrogen bonds, which contribute in the structural stability of peptides. • Chemical reactivity and the physicochemical features are crucial in the biological functions of peptides. - Abstract: Inflammatory response events are initiated by a complex series of molecular reactions that generate chemical intermediaries. The structure and properties of peptides and proteins are determined by the charge distribution of their side chains, which play an essential role in its electronic structure and physicochemical properties, hence on its biological functionality. The aim of this study was to analyze the effect of changing one central amino acid, such as substituting asparagine for aspartic acid, from Cys–Asn–Ser in aqueous solution, by assessing the conformational stability, physicochemical properties, chemical reactivity and their relationship with anti-inflammatory activity; employing quantum-chemical descriptors at the M06-2X/6-311+G(d,p) level. Our results suggest that asparagine plays a more critical role than aspartic acid in the structural stability, physicochemical features, and chemical reactivity of these tripeptides. Substituent groups in the side chain cause significant changes on the conformational stability and chemical reactivity, and consequently on their anti-inflammatory activity.

  3. Chemical Reactive Anchoring Lipids with Different Performance for Cell Surface Re-engineering Application.

    Science.gov (United States)

    Vabbilisetty, Pratima; Boron, Mallorie; Nie, Huan; Ozhegov, Evgeny; Sun, Xue-Long

    2018-02-28

    Introduction of selectively chemical reactive groups at the cell surface enables site-specific cell surface labeling and modification opportunity, thus facilitating the capability to study the cell surface molecular structure and function and the molecular mechanism it underlies. Further, it offers the opportunity to change or improve a cell's functionality for interest of choice. In this study, two chemical reactive anchor lipids, phosphatidylethanolamine-poly(ethylene glycol)-dibenzocyclooctyne (DSPE-PEG 2000 -DBCO) and cholesterol-PEG-dibenzocyclooctyne (CHOL-PEG 2000 -DBCO) were synthesized and their potential application for cell surface re-engineering via lipid fusion were assessed with RAW 264.7 cells as a model cell. Briefly, RAW 264.7 cells were incubated with anchor lipids under various concentrations and at different incubation times. The successful incorporation of the chemical reactive anchor lipids was confirmed by biotinylation via copper-free click chemistry, followed by streptavidin-fluorescein isothiocyanate binding. In comparison, the cholesterol-based anchor lipid afforded a higher cell membrane incorporation efficiency with less internalization than the phospholipid-based anchor lipid. Low cytotoxicity of both anchor lipids upon incorporation into the RAW 264.7 cells was observed. Further, the cell membrane residence time of the cholesterol-based anchor lipid was evaluated with confocal microscopy. This study suggests the potential cell surface re-engineering applications of the chemical reactive anchor lipids.

  4. Chemical Reactive Anchoring Lipids with Different Performance for Cell Surface Re-engineering Application

    Science.gov (United States)

    2018-01-01

    Introduction of selectively chemical reactive groups at the cell surface enables site-specific cell surface labeling and modification opportunity, thus facilitating the capability to study the cell surface molecular structure and function and the molecular mechanism it underlies. Further, it offers the opportunity to change or improve a cell’s functionality for interest of choice. In this study, two chemical reactive anchor lipids, phosphatidylethanolamine–poly(ethylene glycol)–dibenzocyclooctyne (DSPE–PEG2000–DBCO) and cholesterol–PEG–dibenzocyclooctyne (CHOL–PEG2000–DBCO) were synthesized and their potential application for cell surface re-engineering via lipid fusion were assessed with RAW 264.7 cells as a model cell. Briefly, RAW 264.7 cells were incubated with anchor lipids under various concentrations and at different incubation times. The successful incorporation of the chemical reactive anchor lipids was confirmed by biotinylation via copper-free click chemistry, followed by streptavidin-fluorescein isothiocyanate binding. In comparison, the cholesterol-based anchor lipid afforded a higher cell membrane incorporation efficiency with less internalization than the phospholipid-based anchor lipid. Low cytotoxicity of both anchor lipids upon incorporation into the RAW 264.7 cells was observed. Further, the cell membrane residence time of the cholesterol-based anchor lipid was evaluated with confocal microscopy. This study suggests the potential cell surface re-engineering applications of the chemical reactive anchor lipids. PMID:29503972

  5. Evaluation of the chemical reactivity in lignin precursors using the Fukui function.

    Science.gov (United States)

    Martinez, Carmen; Rivera, José L; Herrera, Rafael; Rico, José L; Flores, Nelly; Rutiaga, José G; López, Pablo

    2008-02-01

    The hydroxycinnamyl alcohols: p-coumarol, coniferol and sinapol are considered the basic units and precursors of lignins models. In this work, the specific reactivity of these molecules was studied. We investigate their intrinsic chemical reactivity in terms of the Fukui function, applying the principle of hard and soft acids and bases (HSAB) in the framework of the density functional theory (DFT). Comparisons of their nucleophilic, electrophilic and free radical reactivity show their most probably sites to form linkages among them. It is found that the most reactive sites, for reactions involving free radicals, are the carbons at the beta-position in the p-coumarol and sinapol molecules, whilst the regions around the carbon-oxygen bond of the phenoxyl group are the most reactive in coniferol.

  6. Phase equilibria in chemical reactive fluid mixtures

    International Nuclear Information System (INIS)

    Maurer, Gerd

    2011-01-01

    Downstream processing is a major part of nearly all processes in the chemical industries. Most separation processes in the chemical (and related) industries for fluid mixtures are based on phase equilibrium phenomena. The majority of separation processes can be modelled assuming that chemical reactions are of no (or very minor) importance, i.e., assuming that the overall speciation remains unchanged during a separation process. However, there are also a large number of industrially important processes where the thermodynamic properties are influenced by chemical reactions. The phase equilibrium of chemical reactive mixtures has been a major research area of the author's group over nearly 40 years. In this contribution, three examples from that research are discussed. The first example deals with the vapour phase dimerisation of carboxylic acids and its consequences on phase equilibrium phenomena and phase equilibrium predictions. The second example deals with the solubility of sour gases (e.g., carbon dioxide and sulfur dioxide) in aqueous solutions of ammonia. That topic has been of interest for many years, e.g., in relation with the gasification and liquefaction of coal and, more recently, with the removal of carbon dioxide from flue gas in the 'chilled ammonia process'. The third example deals with phase equilibrium phenomena in aqueous solutions of polyelectrolytes. It deals with the phenomenon of 'counter ion condensation' and methods to model the Gibbs free energy of such solutions.

  7. A Conceptual Framework for Predicting the Toxicity of Reactive Chemicals: Modeling Soft Electrophilicity

    Science.gov (United States)

    Although the literature is replete with QSAR models developed for many toxic effects caused by reversible chemical interactions, the development of QSARs for the toxic effects of reactive chemicals lacks a consistent approach. While limitations exit, an appropriate starting-point...

  8. Unifying principles of irreversibility minimization for efficiency maximization in steady-flow chemically-reactive engines

    International Nuclear Information System (INIS)

    Ramakrishnan, Sankaran; Edwards, Christopher F.

    2014-01-01

    Systems research has led to the conception and development of various steady-flow, chemically-reactive, engine cycles for stationary power generation and propulsion. However, the question that remains unanswered is: What is the maximum-efficiency steady-flow chemically-reactive engine architecture permitted by physics? On the one hand the search for higher-efficiency cycles continues, often involving newer processes and devices (fuel cells, carbon separation, etc.); on the other hand the design parameters for existing cycles are continually optimized in response to improvements in device engineering. In this paper we establish that any variation in engine architecture—parametric change or process-sequence change—contributes to an efficiency increase via one of only two possible ways to minimize total irreversibility. These two principles help us unify our understanding from a large number of parametric analyses and cycle-optimization studies for any steady-flow chemically-reactive engine, and set a framework to systematically identify maximum-efficiency engine architectures. - Highlights: • A unified thermodynamic model to study chemically-reactive engine architectures is developed. • All parametric analyses of efficiency are unified by two irreversibility-minimization principles. • Variations in internal energy transfers yield a net work increase that is greater than engine irreversibility reduced. • Variations in external energy transfers yield a net work increase that is lesser than engine irreversibility reduced

  9. Encoding of Fundamental Chemical Entities of Organic Reactivity Interest using chemical ontology and XML.

    Science.gov (United States)

    Durairaj, Vijayasarathi; Punnaivanam, Sankar

    2015-09-01

    Fundamental chemical entities are identified in the context of organic reactivity and classified as appropriate concept classes namely ElectronEntity, AtomEntity, AtomGroupEntity, FunctionalGroupEntity and MolecularEntity. The entity classes and their subclasses are organized into a chemical ontology named "ChemEnt" for the purpose of assertion, restriction and modification of properties through entity relations. Individual instances of entity classes are defined and encoded as a library of chemical entities in XML. The instances of entity classes are distinguished with a unique notation and identification values in order to map them with the ontology definitions. A model GUI named Entity Table is created to view graphical representations of all the entity instances. The detection of chemical entities in chemical structures is achieved through suitable algorithms. The possibility of asserting properties to the entities at different levels and the mechanism of property flow within the hierarchical entity levels is outlined. Copyright © 2015 Elsevier Inc. All rights reserved.

  10. Modification of chemical reactivity of enzymatic hydrolysis lignin by ultrasound treatment in dilute alkaline solutions.

    Science.gov (United States)

    Ma, Zhuoming; Li, Shujun; Fang, Guizhen; Patil, Nikhil; Yan, Ning

    2016-12-01

    In this study, we have explored various ultrasound treatment conditions for structural modification of enzymatic hydrolysis lignin (EHL) for enhanced chemical reactivity. The key structural modifications were characterized by using a combination of analytical methods, including, Fourier Transform-Infrared spectroscopy (FTIR), Proton Nuclear Magnetic Resonance ( 1 H NMR), Gel permeation chromatography (GPC), X-ray photoelectron spectroscopy (XPS), and Folin-Ciocalteu (F-C) method. Chemical reactivity of the modified EHL samples was determined by both 1,1-diphenyl-2-picrylhydrazyl (DPPH) free radical scavenging activity and their reactivity towards formaldehyde. It was observed that the modified EHL had a higher phenolic hydroxyl group content, a lower molecular weight, a higher reactivity towards formaldehyde, and a greater antioxidant property. The higher reactivity demonstrated by the samples after treatment suggesting that ultrasound is a promising method for modifying enzymatic hydrolysis lignin for value-added applications. Copyright © 2016 Elsevier B.V. All rights reserved.

  11. Chemical reactivity of analogous technetium(V) and rhenium(V) dioxo complexes

    International Nuclear Information System (INIS)

    Kremer, C.; Kremer, E.; Leon, A.

    1993-01-01

    All complexes of the series [MO 2 L 2 ] + (M = Tc, Re, L = ethylenediamine (en), 1,3-diaminopropane (1,3-dap)) have been synthesized and their chemical reactivities investigated. The following properties were studied: stability of the aqueous solutions at different pH values, substitution kinetics, lipophilicity and protein binding. The complexes show very similar reactivity in aqueous solution. From a radiopharmaceutical point of view, no significant difference in their in vivo behavior is expected. (author) 12 refs.; 1 fig.; 3 tabs

  12. Reactive skin decontamination lotion (RSDL) for the decontamination of chemical warfare agent (CWA) dermal exposure.

    Science.gov (United States)

    Schwartz, M D; Hurst, C G; Kirk, M A; Reedy, S J D; Braue, E H

    2012-08-01

    Rapid decontamination of the skin is the single most important action to prevent dermal absorption of chemical contaminants in persons exposed to chemical warfare agents (CWA) and toxic industrial chemicals (TICs) as a result of accidental or intentional release. Chemicals on the skin may be removed by mechanical means through the use of dry sorbents or water. Recent interest in decontamination systems which both partition contaminants away from the skin and actively neutralize the chemical has led to the development of several reactive decontamination solutions. This article will review the recently FDA-approved Reactive Skin Decontamination Lotion (RSDL) and will summarize the toxicity and efficacy studies conducted to date. Evidence of RSDL's superior performance against vesicant and organophosphorus chemical warfare agents compared to water, bleach, and dry sorbents, suggests that RSDL may have a role in mass human exposure chemical decontamination in both the military and civilian arenas.

  13. 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.

  14. Enhancing the design of in situ chemical barriers with multicomponent reactive transport modeling

    International Nuclear Information System (INIS)

    Sevougian, S.D.; Steefel, C.I.; Yabusaki, S.B.

    1994-11-01

    This paper addresses the need for systematic control of field-scale performance in the emplacement and operation of in situ chemical treatment barriers; in particular, it addresses the issue of how the local coupling of reaction kinetics and material heterogeneities at the laboratory or bench scale can be accurately upscaled to the field. The authors have recently developed modeling analysis tools that can explicitly account for all relevant chemical reactions that accompany the transport of reagents and contaminants through a chemically and physically heterogeneous subsurface rock or soil matrix. These tools are incorporated into an enhanced design methodology for in situ chemical treatment technologies, and the new methodology is demonstrated in the ongoing design of a field experiment for the In Situ Redox Manipulation (ISRM) project at the U.S. Department of Energy (DOE) Hanford Site. The ISRM design approach, which systematically integrates bench-scale and site characterization information, provides an ideal test for the new reactive transport techniques. The need for the enhanced chemistry capability is demonstrated by an example that shows how intra-aqueous redox kinetics can affect the transport of reactive solutes. Simulations are carried out on massively parallel computer architectures to resolve the influence of multiscale heterogeneities on multicomponent, multidimensional reactive transport. The technology will soon be available to design larger-scale remediation schemes

  15. Self-organised synthesis of Rh nanostructures with tunable chemical reactivity

    Directory of Open Access Journals (Sweden)

    Lizzit S

    2007-01-01

    Full Text Available AbstractNonequilibrium periodic nanostructures such as nanoscale ripples, mounds and rhomboidal pyramids formed on Rh(110 are particularly interesting as candidate model systems with enhanced catalytic reactivity, since they are endowed with steep facets running along nonequilibrium low-symmetry directions, exposing a high density of undercoordinated atoms. In this review we report on the formation of these novel nanostructured surfaces, a kinetic process which can be controlled by changing parameters such as temperature, sputtering ion flux and energy. The role of surface morphology with respect to chemical reactivity is investigated by analysing the carbon monoxide dissociation probability on the different nanostructured surfaces.

  16. Large-Eddy Simulation of Chemically Reactive Pollutant Transport from a Point Source in Urban Area

    Science.gov (United States)

    Du, Tangzheng; Liu, Chun-Ho

    2013-04-01

    Most air pollutants are chemically reactive so using inert scalar as the tracer in pollutant dispersion modelling would often overlook their impact on urban inhabitants. In this study, large-eddy simulation (LES) is used to examine the plume dispersion of chemically reactive pollutants in a hypothetical atmospheric boundary layer (ABL) in neutral stratification. The irreversible chemistry mechanism of ozone (O3) titration is integrated into the LES model. Nitric oxide (NO) is emitted from an elevated point source in a rectangular spatial domain doped with O3. The LES results are compared well with the wind tunnel results available in literature. Afterwards, the LES model is applied to idealized two-dimensional (2D) street canyons of unity aspect ratio to study the behaviours of chemically reactive plume over idealized urban roughness. The relation among various time scales of reaction/turbulence and dimensionless number are analysed.

  17. The synergistic effect of chemical carcinogens enhances Epstein-Barr virus reactivation and tumor progression of nasopharyngeal carcinoma cells.

    Science.gov (United States)

    Fang, Chih-Yeu; Huang, Sheng-Yen; Wu, Chung-Chun; Hsu, Hui-Yu; Chou, Sheng-Ping; Tsai, Ching-Hwa; Chang, Yao; Takada, Kenzo; Chen, Jen-Yang

    2012-01-01

    Seroepidemiological studies imply a correlation between Epstein-Barr virus (EBV) reactivation and the development of nasopharyngeal carcinoma (NPC). N-nitroso compounds, phorbols, and butyrates are chemicals found in food and herb samples collected from NPC high-risk areas. These chemicals have been reported to be risk factors contributing to the development of NPC, however, the underlying mechanism is not fully understood. We have demonstrated previously that low dose N-methyl-N'-nitro-N-nitrosoguanidine (MNNG, 0.1 µg/ml) had a synergistic effect with 12-O-tetradecanoylphorbol-13-acetate (TPA) and sodium butyrate (SB) in enhancing EBV reactivation and genome instability in NPC cells harboring EBV. Considering that residents in NPC high-risk areas may contact regularly with these chemical carcinogens, it is vital to elucidate the relation between chemicals and EBV and their contributions to the carcinogenesis of NPC. In this study, we constructed a cell culture model to show that genome instability, alterations of cancer hallmark gene expression, and tumorigenicity were increased after recurrent EBV reactivation in NPC cells following combined treatment of TPA/SB and MNNG. NPC cells latently infected with EBV, NA, and the corresponding EBV-negative cell, NPC-TW01, were periodically treated with MNNG, TPA/SB, or TPA/SB combined with MNNG. With chemically-induced recurrent reactivation of EBV, the degree of genome instability was significantly enhanced in NA cells treated with a combination of TPA/SB and MNNG than those treated individually. The Matrigel invasiveness, as well as the tumorigenicity in mouse, was also enhanced in NA cells after recurrent EBV reactivation. Expression profile analysis by microarray indicates that many carcinogenesis-related genes were altered after recurrent EBV reactivation, and several aberrations observed in cell lines correspond to alterations in NPC lesions. These results indicate that cooperation between chemical carcinogens can

  18. Effect of mechanical activation on structure changes and reactivity in further chemical modification of lignin.

    Science.gov (United States)

    Zhao, Xiaohong; Zhang, Yanjuan; Hu, Huayu; Huang, Zuqiang; Yang, Mei; Chen, Dong; Huang, Kai; Huang, Aimin; Qin, Xingzhen; Feng, Zhenfei

    2016-10-01

    Lignin was treated by mechanical activation (MA) in a customized stirring ball mill, and the structure and reactivity in further esterification were studied. The chemical structure and morphology of MA-treated lignin and the esterified products were analyzed by chemical analysis combined with UV/vis spectrometer, FTIR,NMR, SEM and particle size analyzer. The results showed that MA contributed to the increase of aliphatic hydroxyl, phenolic hydroxyl, carbonyl and carboxyl groups but the decrease of methoxyl groups. Moreover, MA led to the decrease of particle size and the increase of specific surface area and roughness of surface in lignin. The reactivity of lignin was enhanced significantly for the increase of hydroxyl content and the improvement of mass transfer in chemical reaction caused by the changes of molecular structure and morphological structure. The process of MA is green and simple, and is an effective method for enhancing the reactivity of lignin. Copyright © 2016 Elsevier B.V. All rights reserved.

  19. Fast screening of analytes for chemical reactions by reactive low-temperature plasma ionization mass spectrometry.

    Science.gov (United States)

    Zhang, Wei; Huang, Guangming

    2015-11-15

    Approaches for analyte screening have been used to aid in the fine-tuning of chemical reactions. Herein, we present a simple and straightforward analyte screening method for chemical reactions via reactive low-temperature plasma ionization mass spectrometry (reactive LTP-MS). Solution-phase reagents deposited on sample substrates were desorbed into the vapor phase by action of the LTP and by thermal desorption. Treated with LTP, both reagents reacted through a vapor phase ion/molecule reaction to generate the product. Finally, protonated reagents and products were identified by LTP-MS. Reaction products from imine formation reaction, Eschweiler-Clarke methylation and the Eberlin reaction were detected via reactive LTP-MS. Products from the imine formation reaction with reagents substituted with different functional groups (26 out of 28 trials) were successfully screened in a time of 30 s each. Besides, two short-lived reactive intermediates of Eschweiler-Clarke methylation were also detected. LTP in this study serves both as an ambient ionization source for analyte identification (including reagents, intermediates and products) and as a means to produce reagent ions to assist gas-phase ion/molecule reactions. The present reactive LTP-MS method enables fast screening for several analytes from several chemical reactions, which possesses good reagent compatibility and the potential to perform high-throughput analyte screening. In addition, with the detection of various reactive intermediates (intermediates I and II of Eschweiler-Clarke methylation), the present method would also contribute to revealing and elucidating reaction mechanisms. Copyright © 2015 John Wiley & Sons, Ltd.

  20. The chemical reactivity and structure of collagen studied by neutron diffraction

    Energy Technology Data Exchange (ETDEWEB)

    Wess, T.J.; Wess, L.; Miller, A. [Univ. of Stirling (United Kingdom)

    1994-12-31

    The chemical reactivity of collagen can be studied using neutron diffraction (a non-destructive technique), for certain reaction types. Collagen contains a number of lysine and hydroxylysine side chains that can react with aldehydes and ketones, or these side chains can themselves be converted to aldehydes by lysyl oxidase. The reactivity of these groups not only has an important role in the maintenance of mechanical strength in collagen fibrils, but can also manifest pathologically in the cases of aging, diabetes (reactivity with a variety of sugars) and alcoholism (reactivity with acetaldehyde). The reactivity of reducing groups with collagen can be studied by neutron diffraction, since the crosslink formed in the adduction process is initially of a Schiff base or keto-imine nature. The nature of this crosslink allows it to be deuterated, and the position of this relatively heavy scattering atom can be used in a process of phase determination by multiple isomorphous replacement. This process was used to study the following: the position of natural crosslinks in collagen; the position of adducts in tendon from diabetic rats in vivo and the in vitro position of acetaidehyde adducts in tendon.

  1. The chemical reactivity and structure of collagen studied by neutron diffraction

    International Nuclear Information System (INIS)

    Wess, T.J.; Wess, L.; Miller, A.

    1994-01-01

    The chemical reactivity of collagen can be studied using neutron diffraction (a non-destructive technique), for certain reaction types. Collagen contains a number of lysine and hydroxylysine side chains that can react with aldehydes and ketones, or these side chains can themselves be converted to aldehydes by lysyl oxidase. The reactivity of these groups not only has an important role in the maintenance of mechanical strength in collagen fibrils, but can also manifest pathologically in the cases of aging, diabetes (reactivity with a variety of sugars) and alcoholism (reactivity with acetaldehyde). The reactivity of reducing groups with collagen can be studied by neutron diffraction, since the crosslink formed in the adduction process is initially of a Schiff base or keto-imine nature. The nature of this crosslink allows it to be deuterated, and the position of this relatively heavy scattering atom can be used in a process of phase determination by multiple isomorphous replacement. This process was used to study the following: the position of natural crosslinks in collagen; the position of adducts in tendon from diabetic rats in vivo and the in vitro position of acetaidehyde adducts in tendon

  2. Deposition of chemically reactive and repellent sites on biosensor chips for reduced non-specific binding.

    Science.gov (United States)

    Gandhiraman, R P; Gubala, V; Le, N C H; Nam, Le Cao Hoai; Volcke, C; Doyle, C; James, B; Daniels, S; Williams, D E

    2010-08-01

    The performances of new polymeric materials with excellent optical properties and good machinability have led the biomedical diagnostics industry to develop cheap disposable biosensor platforms appropriate for point of care applications. Zeonor, a type of cycloolefin polymer (COP), is one such polymer that presents an excellent platform for biosensor chips. These polymer substrates have to be modified to have suitable physico-chemical properties for immobilizing proteins. In this work, we have demonstrated the amine functionalization of COP substrates, by plasma enhanced chemical vapour deposition (PECVD), through codeposition of ethylene diamine and 3-aminopropyltriethoxysilane precursors, for building chemistries on the plastic chip. The elemental composition, adhesion, ageing and reactivity of the plasma polymerized film were examined. The Si-O functionality present in amino silane contributed for a good interfacial adhesion of the coating to COP substrates and also acted as a network building layer for plasma polymerization. Wet chemical modification was then carried out on the amine functionalized chips to create chemically reactive isothiocyanate sites and protein repellent fluorinated sites on the same chip. The density of the reactive and repellent sites was altered by choosing appropriate mixtures of homofunctional phenyldiisothiocyanate (PDITC), pentafluoroisothiocyanate (5FITC) and phenylisothiocyanate (PITC) compounds. By tailoring the density of reactive binding sites and protein repellent sites, the non-specific binding of ssDNA has been decreased to a significant extent. Copyright 2010 Elsevier B.V. All rights reserved.

  3. Chemical Imaging and Dynamical Studies of Reactivity and Emergent Behavior in Complex Interfacial Systems. Final Technical Report

    Energy Technology Data Exchange (ETDEWEB)

    Sibener, Steven J. [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

  4. Reactive hydro- end chlorocarbons in the troposphere and lower stratosphere : sources, distributions, and chemical impact

    NARCIS (Netherlands)

    Scheeren, H.A.

    2003-01-01

    The work presented in this thesis focuses on measurements of chemical reactive C2 C7 non-methane hydrocarbons (NMHC) and C1 C2 chlorocarbons with atmospheric lifetimes of a few hours up to about a year. The group of reactive chlorocarbons includes the most abundant atmospheric species with large

  5. Effect of chemical degradation on fluxes of reactive compounds – a study with a stochastic Lagrangian transport model

    Directory of Open Access Journals (Sweden)

    J. Rinne

    2012-06-01

    Full Text Available In the analyses of VOC fluxes measured above plant canopies, one usually assumes the flux above canopy to equal the exchange at the surface. Thus one assumes the chemical degradation to be much slower than the turbulent transport. We used a stochastic Lagrangian transport model in which the chemical degradation was described as first order decay in order to study the effect of the chemical degradation on above canopy fluxes of chemically reactive species. With the model we explored the sensitivity of the ratio of the above canopy flux to the surface emission on several parameters such as chemical lifetime of the compound, friction velocity, stability, and canopy density. Our results show that friction velocity and chemical lifetime affected the loss during transport the most. The canopy density had a significant effect if the chemically reactive compound was emitted from the forest floor. We used the results of the simulations together with oxidant data measured during HUMPPA-COPEC-2010 campaign at a Scots pine site to estimate the effect of the chemistry on fluxes of three typical biogenic VOCs, isoprene, α-pinene, and β-caryophyllene. Of these, the chemical degradation had a major effect on the fluxes of the most reactive species β-caryophyllene, while the fluxes of α-pinene were affected during nighttime. For these two compounds representing the mono- and sesquiterpenes groups, the effect of chemical degradation had also a significant diurnal cycle with the highest chemical loss at night. The different day and night time loss terms need to be accounted for, when measured fluxes of reactive compounds are used to reveal relations between primary emission and environmental parameters.

  6. Nano-patterning of perpendicular magnetic recording media by low-energy implantation of chemically reactive ions

    International Nuclear Information System (INIS)

    Martin-Gonzalez, M.S.; Briones, F.; Garcia-Martin, J.M.; Montserrat, J.; Vila, L.; Faini, G.; Testa, A.M.; Fiorani, D.; Rohrmann, H.

    2010-01-01

    Magnetic nano-patterning of perpendicular hard disk media with perpendicular anisotropy, but preserving disk surface planarity, is presented here. Reactive ion implantation is used to locally modify the chemical composition (hence the magnetization and magnetic anisotropy) of the Co/Pd multilayer in irradiated areas. The procedure involves low energy, chemically reactive ion irradiation through a resist mask. Among N, P and As ions, P are shown to be most adequate to obtain optimum bit density and topography flatness for industrial Co/Pd multilayer media. The effect of this ion contributes to isolate perpendicular bits by destroying both anisotropy and magnetic exchange in the irradiated areas. Low ion fluences are effective due to the stabilization of atomic displacement levels by the chemical effect of covalent impurities.

  7. 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.)

  8. Reactive chemically modified piezoelectric crystal detectors: A new class of high-selectivity sensors

    International Nuclear Information System (INIS)

    Fadeev, A.Yu.; Filatov, A.L.; Lisichkin, G.V.

    1994-01-01

    A great number of works have focused on the study of properties of modified piezoelectric quartz crystal detectors (PQCDs) coated with sorbing substrates and on applying sensors based on them for the analysis of diluted gas mixtures and solutions. This work offers a new class of gravemetric sensors characterized by a reversible chemical reaction that occurs on their surface. Silica films are proposed as a sorbing coating of quartz detectors, and a chemical modification of a surface is suggested for covalent fixation of the necessary compounds. PQCDs were chemically modified with reactive diene derivatives that can also act as dienophiles. Hexachlorocyclopentadiene (HCCPD, resonater I) and cyclopentadiene (CPD, resonator II) were fixed on a PQCD surface in several stages. After treatment with the resonaters, the PQCD in a CPD gas phase exhibited time dependent frequency shifts from 20-100 Hz. The results suggest that there is a reversible chemical reaction on the electrode surface of resonators I and II when they interact with CPD vapors. Therefore, PQCDs modified with reactive dienes were prepared for the first time and may be employed as selective sensors for CPD

  9. Transport and Reactivity of Decontaminants to Provide Hazard Mitigation of Chemical Warfare Agents from Materials

    Science.gov (United States)

    2016-06-01

    2013 4. TITLE AND SUBTITLE Transport and Reactivity of Decontaminants to Provide Hazard Mitigation of Chemical Warfare Agents from Materials 5a...directions for future decontamination formulation approaches. 15. SUBJECT TERMS GD HD Decontamination Hazard mitigation VX Chemical warfare agent... DECONTAMINANTS TO PROVIDE HAZARD MITIGATION OF CHEMICAL WARFARE AGENTS FROM MATERIALS 1. INTRODUCTION Decontamination of materials is the

  10. Atomistic-level non-equilibrium model for chemically reactive systems based on steepest-entropy-ascent quantum thermodynamics

    International Nuclear Information System (INIS)

    Li, Guanchen; Al-Abbasi, Omar; Von Spakovsky, Michael R

    2014-01-01

    This paper outlines an atomistic-level framework for modeling the non-equilibrium behavior of chemically reactive systems. The framework called steepest- entropy-ascent quantum thermodynamics (SEA-QT) is based on the paradigm of intrinsic quantum thermodynamic (IQT), which is a theory that unifies quantum mechanics and thermodynamics into a single discipline with wide applications to the study of non-equilibrium phenomena at the atomistic level. SEA-QT is a novel approach for describing the state of chemically reactive systems as well as the kinetic and dynamic features of the reaction process without any assumptions of near-equilibrium states or weak-interactions with a reservoir or bath. Entropy generation is the basis of the dissipation which takes place internal to the system and is, thus, the driving force of the chemical reaction(s). The SEA-QT non-equilibrium model is able to provide detailed information during the reaction process, providing a picture of the changes occurring in key thermodynamic properties (e.g., the instantaneous species concentrations, entropy and entropy generation, reaction coordinate, chemical affinities, reaction rate, etc). As an illustration, the SEA-QT framework is applied to an atomistic-level chemically reactive system governed by the reaction mechanism F + H 2 ↔ FH + H

  11. A reaction-based paradigm to model reactive chemical transport in groundwater with general kinetic and equilibrium reactions

    International Nuclear Information System (INIS)

    Zhang, Fan; Yeh, Gour-Tsyh; Parker, Jack C.; Brooks, Scott C; Pace, Molly; Kim, Young Jin; Jardine, Philip M.; Watson, David B.

    2007-01-01

    This paper presents a reaction-based water quality transport model in subsurface flow systems. Transport of chemical species with a variety of chemical and physical processes is mathematically described by M. partial differential equations (PDEs). Decomposition via Gauss-Jordan column reduction of the reaction network transforms M. species reactive transport equations into two sets of equations: a set of thermodynamic equilibrium equations representing NE equilibrium reactions and a set of reactive transport equations of M-NE kinetic-variables involving no equilibrium reactions (a kinetic-variable is a linear combination of species). The elimination of equilibrium reactions from reactive transport equations allows robust and efficient numerical integration. The model solves the PDEs of kinetic-variables rather than individual chemical species, which reduces the number of reactive transport equations and simplifies the reaction terms in the equations. A variety of numerical methods are investigated for solving the coupled transport and reaction equations. Simulation comparisons with exact solutions were performed to verify numerical accuracy and assess the effectiveness of various numerical strategies to deal with different application circumstances. Two validation examples involving simulations of uranium transport in soil columns are presented to evaluate the ability of the model to simulate reactive transport with complex reaction networks involving both kinetic and equilibrium reactions

  12. A reaction-based paradigm to model reactive chemical transport in groundwater with general kinetic and equilibrium reactions.

    Science.gov (United States)

    Zhang, Fan; Yeh, Gour-Tsyh; Parker, Jack C; Brooks, Scott C; Pace, Molly N; Kim, Young-Jin; Jardine, Philip M; Watson, David B

    2007-06-16

    This paper presents a reaction-based water quality transport model in subsurface flow systems. Transport of chemical species with a variety of chemical and physical processes is mathematically described by M partial differential equations (PDEs). Decomposition via Gauss-Jordan column reduction of the reaction network transforms M species reactive transport equations into two sets of equations: a set of thermodynamic equilibrium equations representing N(E) equilibrium reactions and a set of reactive transport equations of M-N(E) kinetic-variables involving no equilibrium reactions (a kinetic-variable is a linear combination of species). The elimination of equilibrium reactions from reactive transport equations allows robust and efficient numerical integration. The model solves the PDEs of kinetic-variables rather than individual chemical species, which reduces the number of reactive transport equations and simplifies the reaction terms in the equations. A variety of numerical methods are investigated for solving the coupled transport and reaction equations. Simulation comparisons with exact solutions were performed to verify numerical accuracy and assess the effectiveness of various numerical strategies to deal with different application circumstances. Two validation examples involving simulations of uranium transport in soil columns are presented to evaluate the ability of the model to simulate reactive transport with complex reaction networks involving both kinetic and equilibrium reactions.

  13. Thermal chemical-mechanical reactive flow model of shock initiation in solid explosives

    International Nuclear Information System (INIS)

    Nicholls, A.L. III; Tarver, C.M.

    1998-01-01

    The three dimensional Arbitrary Lagrange Eulerian hydrodynamic computer code ALE3D with fully coupled thermal-chemical-mechanical material models provides the framework for the development of a physically realistic model of shock initiation and detonation of solid explosives. The processes of hot spot formation during shock compression, subsequent ignition of reaction or failure to react, growth of reaction in individual hot spots, and coalescence of reacting hot spots during the transition to detonation can now be modeled using Arrhenius chemical kinetic rate laws and heat transfer to propagate the reactive flow. This paper discusses the growth rates of reacting hot spots in HMX and TATB and their coalescence during shock to detonation transition. Hot spot deflagration rates are found to be fast enough to consume explosive particles less than 10 mm in diameter during typical shock duration times, but larger particles must fragment and create more reactive surface area in order to be rapidly consumed

  14. Feasibility Study for the Use of Green, Bio-Based, Efficient Reactive Sorbent Material to Neutralize Chemical Warfare Agents

    Science.gov (United States)

    2012-08-02

    REPORT Feasibility study for the use of green, bio-based, efficient reactive sorbent material to neutralize chemical warfare agents 14. ABSTRACT 16...way cellulose, lignin and hemicelluloses interact as well as whole wood dissolution occurs in ILs. The present project was conducted to 1. REPORT...Feasibility study for the use of green, bio-based, efficient reactive sorbent material to neutralize chemical warfare agents Report Title ABSTRACT Over the

  15. Ultraviolet light photobiology of the protozoan Tetrahymena pyriformis and chemical reactivation of DNA damage

    International Nuclear Information System (INIS)

    Wheeler, J.S.

    1988-01-01

    The tunable dye laser was developed in order to perform UV-B and UV-C (254-320 nm) action spectra studies on several different organisms. Using the laser, action spectra studies have been performed for Escherichia coli, Saccharomyces, Chlamydomonas, Caenorhabditis elegans, Paramecium, and Tetrahymena pyriformis. Studies generally indicate increasing LD 50 values with increasing wavelength. Two notable findings were made: (1) The action spectra does not follow the DNA absorption spectra at 280, 290 and 295 nm; (2) The repair competent/repair defective sensitization factor does not remain constant throughout the wavelength region. In addition it was found that the repair defective strain of E. coli, Bs-1, showed an increase in survival with increasing UV irradiation, at certain dose levels. Further experiments were designed to better characterize the reactivation. Tetrahymena were exposed to UV-C and reactivated with methyl methanesulfonate (MMS) and 4-nitro quinoline oxide (4-NQO). In both cases survival was seen to increase after chemical exposure. Likewise, UV-C was found to reactivate chemical damage (MMS)

  16. Modeling non-isothermal multiphase multi-species reactive chemical transport in geologic media

    Energy Technology Data Exchange (ETDEWEB)

    Tianfu Xu; Gerard, F.; Pruess, K.; Brimhall, G.

    1997-07-01

    The assessment of mineral deposits, the analysis of hydrothermal convection systems, the performance of radioactive, urban and industrial waste disposal, the study of groundwater pollution, and the understanding of natural groundwater quality patterns all require modeling tools that can consider both the transport of dissolved species as well as their interactions with solid (or other) phases in geologic media and engineered barriers. Here, a general multi-species reactive transport formulation has been developed, which is applicable to homogeneous and/or heterogeneous reactions that can proceed either subject to local equilibrium conditions or kinetic rates under non-isothermal multiphase flow conditions. Two numerical solution methods, the direct substitution approach (DSA) and sequential iteration approach (SIA) for solving the coupled complex subsurface thermo-physical-chemical processes, are described. An efficient sequential iteration approach, which solves transport of solutes and chemical reactions sequentially and iteratively, is proposed for the current reactive chemical transport computer code development. The coupled flow (water, vapor, air and heat) and solute transport equations are also solved sequentially. The existing multiphase flow code TOUGH2 and geochemical code EQ3/6 are used to implement this SIA. The flow chart of the coupled code TOUGH2-EQ3/6, required modifications of the existing codes and additional subroutines needed are presented.

  17. Chemical reactivation of resin-embedded pHuji adds red for simultaneous two-color imaging with EGFP

    Science.gov (United States)

    Guo, Wenyan; Liu, Xiuli; Liu, Yurong; Gang, Yadong; He, Xiaobin; Jia, Yao; Yin, Fangfang; Li, Pei; Huang, Fei; Zhou, Hongfu; Wang, Xiaojun; Gong, Hui; Luo, Qingming; Xu, Fuqiang; Zeng, Shaoqun

    2017-01-01

    The pH-sensitive fluorescent proteins enabling chemical reactivation in resin are useful tools for fluorescence microimaging. EGFP or EYFP is good for such applications. For simultaneous two-color imaging, a suitable red fluorescent protein is an urgent need. Here a pH-sensitive red fluorescent protein, pHuji, is selected and verified to remain pH-sensitive in HM20 resin. We observe 183% fluorescence intensity of pHuji in resin-embeded mouse brain and 29.08-fold fluorescence intensity of reactivated pHuji compared to the quenched state. pHuji and EGFP can be quenched and chemically reactivated simultaneously in resin, thus enabling simultaneous two-color micro-optical sectioning tomography of resin-embedded mouse brain. This method may greatly facilitate the visualization of neuronal morphology and neural circuits to promote understanding of the structure and function of the brain. PMID:28717566

  18. Prediction of monomer reactivity in radical copolymerizations from transition state quantum chemical descriptors

    Directory of Open Access Journals (Sweden)

    Zhengde Tan

    2013-01-01

    Full Text Available In comparison with the Q-e scheme, the Revised Patterns Scheme: the U, V Version (the U-V scheme has greatly improved both its accessibility and its accuracy in interpreting and predicting the reactivity of a monomer in free-radical copolymerizations. Quantitative structure-activity relationship (QSAR models were developed to predict the reactivity parameters u and v of the U-V scheme, by applying genetic algorithm (GA and support vector machine (SVM techniques. Quantum chemical descriptors used for QSAR models were calculated from transition state species with structures C¹H3 - C²HR³• or •C¹H2 - C²H2R³ (formed from vinyl monomers C¹H²=C²HR³ + H•, using density functional theory (DFT, at the UB3LYP level of theory with 6-31G(d basis set. The optimum support vector regression (SVR model of the reactivity parameter u based on Gaussian radial basis function (RBF kernel (C = 10, ε = 10- 5 and γ = 1.0 produced root-mean-square (rms errors for the training, validation and prediction sets being 0.220, 0.326 and 0.345, respectively. The optimal SVR model for v with the RBF kernel (C = 20, ε = 10- 4 and γ = 1.2 produced rms errors for the training set of 0.123, the validation set of 0.206 and the prediction set of 0.238. The feasibility of applying the transition state quantum chemical descriptors to develop SVM models for reactivity parameters u and v in the U-V scheme has been demonstrated.

  19. Chemical reactivity of potential ferrocyanide precipitates in Hanford tanks with nitrates and nitrites

    International Nuclear Information System (INIS)

    Scheele, R.D.; Burger, L.L.; Tingey, J.M.; Hallen, R.T.; Lilga, M.A.

    1992-01-01

    Ferrocyanide-bearing wastes were produced at the Hanford Site during the 1950s. Safe storage of these wastes has recently drawn increased attention. As a result of these concerns, the Pacific Northwest Laboratory was chartered to investigate the chemical reactivity and explosivity of the ferrocyanide-bearing wastes. We have investigated the thermal sensitivity of synthetic wastes and ferrocyanides and observed oxidation at 130 deg. C and explosions down to 295 deg. C. Coupled with thermodynamic calculations, these thermal studies have also shown a dependence of the reactivity on the synthetic waste composition, which is dependent on the solids settling behavior. (author)

  20. To Model Chemical Reactivity in Heterogeneous Emulsions, Think Homogeneous Microemulsions.

    Science.gov (United States)

    Bravo-Díaz, Carlos; Romsted, Laurence Stuart; Liu, Changyao; Losada-Barreiro, Sonia; Pastoriza-Gallego, Maria José; Gao, Xiang; Gu, Qing; Krishnan, Gunaseelan; Sánchez-Paz, Verónica; Zhang, Yongliang; Dar, Aijaz Ahmad

    2015-08-25

    Two important and unsolved problems in the food industry and also fundamental questions in colloid chemistry are how to measure molecular distributions, especially antioxidants (AOs), and how to model chemical reactivity, including AO efficiency in opaque emulsions. The key to understanding reactivity in organized surfactant media is that reaction mechanisms are consistent with a discrete structures-separate continuous regions duality. Aggregate structures in emulsions are determined by highly cooperative but weak organizing forces that allow reactants to diffuse at rates approaching their diffusion-controlled limit. Reactant distributions for slow thermal bimolecular reactions are in dynamic equilibrium, and their distributions are proportional to their relative solubilities in the oil, interfacial, and aqueous regions. Our chemical kinetic method is grounded in thermodynamics and combines a pseudophase model with methods for monitoring the reactions of AOs with a hydrophobic arenediazonium ion probe in opaque emulsions. We introduce (a) the logic and basic assumptions of the pseudophase model used to define the distributions of AOs among the oil, interfacial, and aqueous regions in microemulsions and emulsions and (b) the dye derivatization and linear sweep voltammetry methods for monitoring the rates of reaction in opaque emulsions. Our results show that this approach provides a unique, versatile, and robust method for obtaining quantitative estimates of AO partition coefficients or partition constants and distributions and interfacial rate constants in emulsions. The examples provided illustrate the effects of various emulsion properties on AO distributions such as oil hydrophobicity, emulsifier structure and HLB, temperature, droplet size, surfactant charge, and acidity on reactant distributions. Finally, we show that the chemical kinetic method provides a natural explanation for the cut-off effect, a maximum followed by a sharp reduction in AO efficiency with

  1. Atomic-level spatial distributions of dopants on silicon surfaces: toward a microscopic understanding of surface chemical reactivity

    Science.gov (United States)

    Hamers, Robert J.; Wang, Yajun; Shan, Jun

    1996-11-01

    We have investigated the interaction of phosphine (PH 3) and diborane (B 2H 6) with the Si(001) surface using scanning tunneling microscopy, infrared spectroscopy, and ab initio molecular orbital calculations. Experiment and theory show that the formation of PSi heterodimers is energetically favorable compared with formation of PP dimers. The stability of the heterodimers arises from a large strain energy associated with formation of PP dimers. At moderate P coverages, the formation of PSi heterodimers leaves the surface with few locations where there are two adjacent reactive sites. This in turn modifies the chemical reactivity toward species such as PH 3, which require only one site to adsorb but require two adjacent sites to dissociate. Boron on Si(001) strongly segregates into localized regions of high boron concentration, separated by large regions of clean Si. This leads to a spatially-modulated chemical reactivity which during subsequent growth by chemical vapor deposition (CVD) leads to formation of a rough surface. The implications of the atomic-level spatial distribution of dopants on the rates and mechanisms of CVD growth processes are discussed.

  2. Chemical composition and photochemical reactivity of exhaust from aircraft turbine engines

    Directory of Open Access Journals (Sweden)

    C. W. Spicer

    1994-08-01

    Full Text Available Assessment of the environmental impact of aircraft emissions is required by planners and policy makers. Seveal areas of concern are: 1. exposure of airport workers and urban residents to toxic chemicals emitted when the engines operate at low power (idle and taxi on the ground; 2. contributions to urban photochemical air pollution of aircraft volatile organic and nitrogen oxides emissions from operations around airports; and 3. emissions of nitrogen oxides and particles during high-altitude operation. The environmental impact of chemicals emitted from jet aircraft turbine engines has not been firmly established due to lack of data regarding emission rates and identities of the compounds emitted. This paper describes an experimental study of two different aircraft turbine engines designed to determine detailed organic emissions, as well as emissions of inorganic gases. Emissions were measured at several engine power settings. Measurements were made of detailed organic composition from C1 through C17, CO, CO2, NO, NOx, and polycyclic aromatic hydrocarbons. Measurements were made using a multi-port sampling pro be positioned directly behind the engine in the exhaust exit plane. The emission measurements have been used to determine the organic distribution by carbon number and the distribution by compound class at each engine power level. The sum of the organic species was compared with an independent measurement of total organic carbon to assess the carbon mass balance. A portion of the exhaust was captured and irradiated in outdoor smog chambers to assess the photochemical reactivity of the emissions with respect to ozone formation. The reactivity of emissions from the two engines was apportioned by chemical compound class.

  3. Chemical composition and photochemical reactivity of exhaust from aircraft turbine engines

    Directory of Open Access Journals (Sweden)

    T. F. Lyon

    Full Text Available Assessment of the environmental impact of aircraft emissions is required by planners and policy makers. Seveal areas of concern are: 1. exposure of airport workers and urban residents to toxic chemicals emitted when the engines operate at low power (idle and taxi on the ground; 2. contributions to urban photochemical air pollution of aircraft volatile organic and nitrogen oxides emissions from operations around airports; and 3. emissions of nitrogen oxides and particles during high-altitude operation. The environmental impact of chemicals emitted from jet aircraft turbine engines has not been firmly established due to lack of data regarding emission rates and identities of the compounds emitted. This paper describes an experimental study of two different aircraft turbine engines designed to determine detailed organic emissions, as well as emissions of inorganic gases. Emissions were measured at several engine power settings. Measurements were made of detailed organic composition from C1 through C17, CO, CO2, NO, NOx, and polycyclic aromatic hydrocarbons. Measurements were made using a multi-port sampling pro be positioned directly behind the engine in the exhaust exit plane. The emission measurements have been used to determine the organic distribution by carbon number and the distribution by compound class at each engine power level. The sum of the organic species was compared with an independent measurement of total organic carbon to assess the carbon mass balance. A portion of the exhaust was captured and irradiated in outdoor smog chambers to assess the photochemical reactivity of the emissions with respect to ozone formation. The reactivity of emissions from the two engines was apportioned by chemical compound class.

  4. Theoretical study of some aspects of the nucleo-bases reactivity: definition of new theoretical tools for the study of chemical reactivity

    International Nuclear Information System (INIS)

    Labet, V.

    2009-09-01

    In this work, three kinds of nucleo-base damages were studied from a theoretical point of view with quantum chemistry methods based on the density-functional theory: the spontaneous deamination of cytosine and its derivatives, the formation of tandem lesion induced by hydroxyl radicals in anaerobic medium and the formation of pyrimidic dimers under exposition to an UV radiation. The complementary use of quantitative static methods allowing the exploration of the potential energy surface of a chemical reaction, and of 'conceptual DFT' principles, leads to information concerning the mechanisms involved and to the rationalization of the differences in the nucleo-bases reactivity towards the formation of a same kind of damage. At the same time, a reflexion was undertaken on the asynchronous concerted mechanism concept, in terms of physical meaning of the transition state, respect of the Maximum Hardness Principle, and determination of the number of primitive processes involved. Finally, a new local reactivity index was developed, relevant to understand the reactivity of a molecular system in an excited state. (author)

  5. Reactive dispersive contaminant transport in coastal aquifers: Numerical simulation of a reactive Henry problem

    KAUST Repository

    Nick, H.M.

    2013-02-01

    The reactive mixing between seawater and terrestrial water in coastal aquifers influences the water quality of submarine groundwater discharge. While these waters come into contact at the seawater groundwater interface by density driven flow, their chemical components dilute and react through dispersion. A larger interface and wider mixing zone may provide favorable conditions for the natural attenuation of contaminant plumes. It has been claimed that the extent of this mixing is controlled by both, porous media properties and flow conditions. In this study, the interplay between dispersion and reactive processes in coastal aquifers is investigated by means of numerical experiments. Particularly, the impact of dispersion coefficients, the velocity field induced by density driven flow and chemical component reactivities on reactive transport in such aquifers is studied. To do this, a hybrid finite-element finite-volume method and a reactive simulator are coupled, and model accuracy and applicability are assessed. A simple redox reaction is considered to describe the degradation of a contaminant which requires mixing of the contaminated groundwater and the seawater containing the terminal electron acceptor. The resulting degradation is observed for different scenarios considering different magnitudes of dispersion and chemical reactivity. Three reactive transport regimes are found: reaction controlled, reaction-dispersion controlled and dispersion controlled. Computational results suggest that the chemical components\\' reactivity as well as dispersion coefficients play a significant role on controlling reactive mixing zones and extent of contaminant removal in coastal aquifers. Further, our results confirm that the dilution index is a better alternative to the second central spatial moment of a plume to describe the mixing of reactive solutes in coastal aquifers. © 2012 Elsevier B.V.

  6. Evaluation of a high-throughput peptide reactivity format assay for assessment of the skin sensitization potential of chemicals

    Directory of Open Access Journals (Sweden)

    Chin Lin eWong

    2016-03-01

    Full Text Available The direct peptide reactivity assay (DPRA is a validated method for in vitro assessment of the skin sensitization potential of chemicals. In the present work, we describe a peptide reactivity assay using 96-well plate format and systematically identified the optimal assay conditions for accurate and reproducible classification of chemicals with known sensitizing capacity. The aim of the research is to ensure that the analytical component of the peptide reactivity assay is robust, accurate and reproducible in accordance with criteria that are used for the validation of bioanalytical methods. Analytical performance was evaluated using quality control samples (QCs; heptapeptides at low, medium and high concentrations and incubation of control chemicals (chemicals with known sensitization capacity, weak, moderate, strong, extreme and non-sensitizers with each of three synthetic heptapeptides, viz Cor1-C420 (Ac-NKKCDLF, cysteine- (Ac-RFAACAA and lysine- (Ac-RFAAKAA containing heptapeptides. The optimal incubation temperature for all three heptapeptides was 25°C. Apparent heptapeptide depletion was affected by vial material composition. Incubation of test chemicals with Cor1-C420, showed that peptide depletion was unchanged in polypropylene vials over 3-days storage in an autosampler but this was not the case for borosilicate glass vials. For cysteine-containing heptapeptide, the concentration was not stable by day 3 post-incubation in borosilicate glass vials. Although the lysine-containing heptapeptide concentration was unchanged in both polypropylene and borosilicate glass vials, the apparent extent of lysine-containing heptapeptide depletion by ethyl acrylate, differed between polypropylene (24.7% and glass (47.3% vials. Additionally, the peptide-chemical complexes for Cor1-C420-cinnamaldehyde and cysteine-containing heptapeptide-2,4-dinitrochlorobenzene were partially reversible during 3-days of autosampler storage. These observations further

  7. Simultaneous measurements of reactive scalar and velocity in a planar liquid jet with a second-order chemical reaction

    Energy Technology Data Exchange (ETDEWEB)

    Watanabe, Tomoaki; Sakai, Yasuhiko; Nagata, Kouji; Terashima, Osamu [Nagoya University, Department of Mechanical Science and Engineering, Nagoya (Japan); Kubo, Takashi [Meijo University, Faculty of Science and Technology, Nagoya (Japan)

    2012-11-15

    This paper presents a new experimental approach for simultaneous measurements of velocity and concentration in a turbulent liquid flow with a chemical reaction. For the simultaneous measurements, we developed a combined probe consisting of an I-type hot-film probe and an optical fiber probe based on the light absorption spectrometric method. In a turbulent planar liquid jet with a second-order chemical reaction (A+B{yields}R), streamwise velocity and concentrations of all reactive species are measured by the combined probe. The turbulent mass fluxes of the reactive species are estimated from the simultaneous measurements. The results show that the influence of the chemical reaction on the turbulent mass flux of the reactant species near the jet exit is different from its influence in other regions, and the turbulent mass flux of the product species has a negative value near the jet exit and a positive value in other regions. (orig.)

  8. Chemical reactivity of alkali lignin modified with laccase

    International Nuclear Information System (INIS)

    Sun, Yong; Qiu, Xueqing; Liu, Yunquan

    2013-01-01

    The modification of alkali lignin with laccase was investigated. The structural change of lignin was analyzed. The sulfonation reactivity was measured by the content of sulfonic group. The results showed the sulfonation reactivity increased to some extent under the condition of atmosphere pressure, but decreased under the condition of 0.3 MPa oxygen pressure. The analysis of Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance (NMR) and gel permeation chromatography (GPC) showed the cleavage of various ether linkages and demethylation took place in the structure of lignin to certain extent during modification with laccase, which contributed to the improvement of sulfonation reactivity. Under the condition of 0.3 MPa oxygen pressure, the ratio of s/g (guaiacyl/syringyl) increased after modification, which reduced the sulfonation reactivity of lignin. Simultaneously partial polymerization reaction, such as 4-O-5′, β-5, 5-5 and other reaction in the aromatic ring decreased the activity sites of C 2 , C 5 and C 6 . Abundant polymerization reaction of α-O increased steric hindrance of C 2 and C 6 in aromatic ring, resulting in low sulfonation reactivity of lignin. -- Highlights: ► The modification of alkali lignin with laccase was investigated. ► The sulfonation reactivity increased under the condition of atmosphere pressure. ► More content of guaiacyl and hydroxy, the less content of methoxyl, syringyl can enhance the sulfonation reactivity of lignin. ► Partial moieties polymerized each other with α-O linkgages during treatment with laccase under oxygen pressure. ► The steric hindrance on C 2 and C 6 in aromatic ring resulted in low sulfonation reaction reactivity of lignin

  9. Influence of the physicochemical and aromatic properties on the chemical reactivity and its relation with carcinogenic and anticoagulant effect of 17β-aminoestrogens

    Energy Technology Data Exchange (ETDEWEB)

    Soriano-Correa, Catalina, E-mail: socc@puma2.zaragoza.unam.mx [Química Computacional, FES-Zaragoza, Universidad Nacional Autónoma de México (UNAM), Iztapalapa, Mexico City (Mexico); Raya, Angélica [Unidad Profesional Interdisciplinaria de Ingeniería Campus Guanajuato, Instituto Politécnico Nacional (IPN), Silao de la Victoria, Guanajuato (Mexico); Barrientos-Salcedo, Carolina [Laboratorio de Química Médica y Quimiogenómica, Facultad de Bioanálisis Campus Veracruz - Boca del Río, Universidad Veracruzana, Veracruz (Mexico); Esquivel, Rodolfo O. [Departamento de Química, Universidad Autónoma Metropolitana-Iztapalapa (UAM-Iztapalapa), Mexico City (Mexico)

    2014-06-25

    Highlights: • The aromatic A-ring of 17β-aminoestrogens contribute to its anticoagulant effect. • The electron-donor substituent groups favored the basicity of 17β-aminoestrogens. • The physicochemical properties are important in the carcinogenic effect of anticoagulant molecules. - Abstract: Activity of steroid hormones is dependent upon a number of factors, as solubility, transport and metabolism. The functional differences caused by structural modifications could exert an influence on the chemical reactivity and biological effect. The goal of this work is to study the influence of the physicochemical and aromatic properties on the chemical reactivity and its relation with the carcinogenic risk that can associate with the anticoagulant effect of 17β-aminoestrogens using quantum-chemical descriptors at the DFT-B3LYP, BH and HLYP and M06-2X levels. The relative acidity of (H1) of the hydroxyl group increases with electron-withdrawing groups. Electron-donor groups favor the basicity. The steric hindrance of the substituents decreases the aromatic character and consequently diminution the carcinogenic effect. Density descriptors: hardness, electrophilic index, atomic charges, molecular orbitals, electrostatic potential and their geometric parameters permit analyses of the chemical reactivity and physicochemical features and to identify some reactive sites of 17β-aminoestrogens.

  10. A comparative study of changes in immunological reactivity during prolonged introduction of radioactive and chemical substances into the organism with drinking water

    International Nuclear Information System (INIS)

    Shubik, V.M.; Nevstrueva, M.A.; Kalnitskij, S.A.; Livshits, R.E.; Merkushev, G.N.; Pilshchik, E.M.; Ponomareva, T.V.

    1978-01-01

    A comparative study was conducted into the factors of non-specific protection and specific immunity, allergic and autoallergic reactivities during prolonged exposure of experimental animals to 6 different radioactive and 7 harmful chemical substances. Qualitative and quantitative peculiarities were found in the changes in immunological reactivity during the exposure of the organism to radionuclides and stable chemical compounds. Impairment of immunity plays an essential role in the course and the outcome of effects induced by chronic action of the substances examined. (author)

  11. Properties of amorphous silicon thin films synthesized by reactive particle beam assisted chemical vapor deposition

    International Nuclear Information System (INIS)

    Choi, Sun Gyu; Wang, Seok-Joo; Park, Hyeong-Ho; Jang, Jin-Nyoung; Hong, MunPyo; Kwon, Kwang-Ho; Park, Hyung-Ho

    2010-01-01

    Amorphous silicon thin films were formed by chemical vapor deposition of reactive particle beam assisted inductively coupled plasma type with various reflector bias voltages. During the deposition, the substrate was heated at 150 o C. The effects of reflector bias voltage on the physical and chemical properties of the films were systematically studied. X-ray diffraction and Raman spectroscopy results showed that the deposited films were amorphous and the films under higher reflector voltage had higher internal energy to be easily crystallized. The chemical state of amorphous silicon films was revealed as metallic bonding of Si atoms by using X-ray photoelectron spectroscopy. An increase in reflector voltage induced an increase of surface morphology of films and optical bandgap and a decrease of photoconductivity.

  12. Chemically reactive species in liquids generated by atmospheric-pressure plasmas and their roles in plasma medicine

    International Nuclear Information System (INIS)

    Hamaguchi, Satoshi

    2013-01-01

    Plasmas whose gas temperatures are close to room temperature may be generated in ambient air or a gas at atmospheric pressure with the use of low-frequency high voltage or low-power radio-frequency (RF) or microwave power applied to electrodes. Such plasmas can serve as a powerful source of free radicals and/or chemically reactive species that arise from atoms and molecules of the ambient gas. Recently use of such plasmas for medical purposes has attracted much attention as they can be implemented in possible medical devices that can cause blood coagulation, heal wounds, facilitate angiogenesis, sterilize surgical devices as well as living tissues without harming healthy cells, and selectively inactivate cancer cells. Especially of interest among reactive species generated by atmospheric-pressure plasmas (APP) are reactive oxygen species (ROS) and reactive nitrogen species (RNS) that are generated in liquid phase. Since most living tissues and cells are immersed in liquids (such as blood or culture media), reactive species generated by APPs in the gas phase are transported to the liquid phase and possibly converted to different types of reactive species therein before causing some influence on the tissues or cells. In this study, the rate equations are solved to evaluate concentrations of various reactive species in pure water that are originated by plasma reactions in atmosphere and possible effects of such species (including ROS/RNS) on living tissues and cells are discussed

  13. Chemically reactive species in liquids generated by atmospheric-pressure plasmas and their roles in plasma medicine

    Energy Technology Data Exchange (ETDEWEB)

    Hamaguchi, Satoshi [Center for Atomic and Molecular Technologies, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871 (Japan)

    2013-07-11

    Plasmas whose gas temperatures are close to room temperature may be generated in ambient air or a gas at atmospheric pressure with the use of low-frequency high voltage or low-power radio-frequency (RF) or microwave power applied to electrodes. Such plasmas can serve as a powerful source of free radicals and/or chemically reactive species that arise from atoms and molecules of the ambient gas. Recently use of such plasmas for medical purposes has attracted much attention as they can be implemented in possible medical devices that can cause blood coagulation, heal wounds, facilitate angiogenesis, sterilize surgical devices as well as living tissues without harming healthy cells, and selectively inactivate cancer cells. Especially of interest among reactive species generated by atmospheric-pressure plasmas (APP) are reactive oxygen species (ROS) and reactive nitrogen species (RNS) that are generated in liquid phase. Since most living tissues and cells are immersed in liquids (such as blood or culture media), reactive species generated by APPs in the gas phase are transported to the liquid phase and possibly converted to different types of reactive species therein before causing some influence on the tissues or cells. In this study, the rate equations are solved to evaluate concentrations of various reactive species in pure water that are originated by plasma reactions in atmosphere and possible effects of such species (including ROS/RNS) on living tissues and cells are discussed.

  14. Young Investigator Proposal, Research Area 7.4 Reactive Chemical Systems: Multifunctional, Bimetallic Nanomaterials Prepared by Atomic Layer Electroless Deposition

    Science.gov (United States)

    2017-09-30

    Report: Young Investigator Proposal, Research Area 7.4 Reactive Chemical Systems: Multifunctional, Bimetallic Nanomaterials Prepared by Atomic Layer ...Chemical Systems: Multifunctional, Bimetallic Nanomaterials Prepared by Atomic Layer Electroless Deposition Report Term: 0-Other Email: pcappillino... Layer Electroless Deposition (ALED, Figure 1) is the ability to tune growth mechanism, hence growth morphology, by altering conditions. In this

  15. Computer tool to evaluate the cue reactivity of chemically dependent individuals.

    Science.gov (United States)

    Silva, Meire Luci da; Frère, Annie France; Oliveira, Henrique Jesus Quintino de; Martucci Neto, Helio; Scardovelli, Terigi Augusto

    2017-03-01

    Anxiety is one of the major influences on the dropout of relapse and treatment of substance abuse treatment. Chemically dependent individuals need (CDI) to be aware of their emotional state in situations of risk during their treatment. Many patients do not agree with the diagnosis of the therapist when considering them vulnerable to environmental stimuli related to drugs. This research presents a cue reactivity detection tool based on a device acquiring physiological signals connected to personal computer. Depending on the variations of the emotional state of the drug addict, alteration of the physiological signals will be detected by the computer tool (CT) which will modify the displayed virtual sets without intervention of the therapist. Developed in 3ds Max® software, the CT is composed of scenarios and objects that are in the habit of marijuana and cocaine dependent individual's daily life. The interaction with the environment is accomplished using a Human-Computer Interface (HCI) that converts incoming physiological signals indicating anxiety state into commands that change the scenes. Anxiety was characterized by the average variability from cardiac and respiratory rate of 30 volunteers submitted stress environment situations. To evaluate the effectiveness of cue reactivity a total of 50 volunteers who were marijuana, cocaine or both dependent were accompanied. Prior to CT, the results demonstrated a poor correlation between the therapists' predictions and those of the chemically dependent individuals. After exposure to the CT, there was a significant increase of 73% in awareness of the risks of relapse. We confirmed the hypothesis that the CT, controlled only by physiological signals, increases the perception of vulnerability to risk situations of individuals with dependence on marijuana, cocaine or both. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

  16. A coupling alternative to reactive transport simulations for long-term prediction of chemical reactions in heterogeneous CO2 storage systems

    Directory of Open Access Journals (Sweden)

    M. De Lucia

    2015-02-01

    Full Text Available Fully coupled, multi-phase reactive transport simulations of CO2 storage systems can be approximated by a simplified one-way coupling of hydrodynamics and reactive chemistry. The main characteristics of such systems, and hypotheses underlying the proposed alternative coupling, are (i that the presence of CO2 is the only driving force for chemical reactions and (ii that its migration in the reservoir is only marginally affected by immobilisation due to chemical reactions. In the simplified coupling, the exposure time to CO2 of each element of the hydrodynamic grid is estimated by non-reactive simulations and the reaction path of one single batch geochemical model is applied to each grid element during its exposure time. In heterogeneous settings, analytical scaling relationships provide the dependency of velocity and amount of reactions to porosity and gas saturation. The analysis of TOUGHREACT fully coupled reactive transport simulations of CO2 injection in saline aquifer, inspired to the Ketzin pilot site (Germany, both in homogeneous and heterogeneous settings, confirms that the reaction paths predicted by fully coupled simulations in every element of the grid show a high degree of self-similarity. A threshold value for the minimum concentration of dissolved CO2 considered chemically active is shown to mitigate the effects of the discrepancy between dissolved CO2 migration in non-reactive and fully coupled simulations. In real life, the optimal threshold value is unknown and has to be estimated, e.g. by means of 1-D or 2-D simulations, resulting in an uncertainty ultimately due to the process de-coupling. However, such uncertainty is more than acceptable given that the alternative coupling enables using grids of the order of millions of elements, profiting from much better description of heterogeneous reservoirs at a fraction of the calculation time of fully coupled models.

  17. Nondestructive Reactivation of Chemical Protective Garments

    National Research Council Canada - National Science Library

    Chang, Kuo

    1995-01-01

    .... Complete reactivation was achieved when the aqueous/ i-propanol/ iodine displacement method of Manes, which removed all but pure hydrocarbon oil soils from the current overgarment Type III foam...

  18. Parameters estimation for reactive transport: A way to test the validity of a reactive model

    Science.gov (United States)

    Aggarwal, Mohit; Cheikh Anta Ndiaye, Mame; Carrayrou, Jérôme

    The chemical parameters used in reactive transport models are not known accurately due to the complexity and the heterogeneous conditions of a real domain. We will present an efficient algorithm in order to estimate the chemical parameters using Monte-Carlo method. Monte-Carlo methods are very robust for the optimisation of the highly non-linear mathematical model describing reactive transport. Reactive transport of tributyltin (TBT) through natural quartz sand at seven different pHs is taken as the test case. Our algorithm will be used to estimate the chemical parameters of the sorption of TBT onto the natural quartz sand. By testing and comparing three models of surface complexation, we show that the proposed adsorption model cannot explain the experimental data.

  19. Chemical stability of reactive skin decontamination lotion (RSDL®).

    Science.gov (United States)

    Bogan, R; Maas, H J; Zimmermann, T

    2018-09-01

    Reactive Skin Decontamination Lotion (RSDL ® ) is used for the decontamination of Chemical Warfare Agents and Toxic Industrial Compounds after dermal exposure. It has to be stockpiled over a long period and is handled in all climatic zones. Therefore stability is an essential matter of concern. In this work we describe a study to the chemical stability of RSDL ® as basis for an estimation of shelf life. We analysed RSDL ® for the active ingredient 2,3-butandione monoxime (diacetylmonooxime, DAM), the putative degradation product dimethylglyoxime (DMG) and unknown degradation products by means of a reversed phase high pressure liquid chromatography (HPLC). Calculations were done according to the Arrhenius equation. Based on the temperature dependent rate constants, the time span was calculated, until defined threshold values for DAM and DMG subject to specification and valid regulations were exceeded. The calculated data were compared to the ones gathered from stockpiled samples and samples exposed during foreign mission. The decline of DAM followed first order kinetics, while formation of DMG could be described by zero order kinetics. The rate constants were distinctively temperature dependent. Calculated data were in good accordance to the measured ones from stockpile and mission. Based on a specified acceptable DAM-content of 90% and a valid threshold value of 0.1% (w/w) for the degradation product DMG, RSDL ® proved to be stable for at least four years if stored at the recommended conditions of 15°C-30°C. If continuously stored at higher temperatures shelf life will decrease markedly. Therefore RSDL ® is an object for risk orientated quality monitoring during storage. Copyright © 2017 Elsevier B.V. All rights reserved.

  20. Computational Study of Chemical Reactivity Using Information-Theoretic Quantities from Density Functional Reactivity Theory for Electrophilic Aromatic Substitution Reactions.

    Science.gov (United States)

    Wu, Wenjie; Wu, Zemin; Rong, Chunying; Lu, Tian; Huang, Ying; Liu, Shubin

    2015-07-23

    The electrophilic aromatic substitution for nitration, halogenation, sulfonation, and acylation is a vastly important category of chemical transformation. Its reactivity and regioselectivity is predominantly determined by nucleophilicity of carbon atoms on the aromatic ring, which in return is immensely influenced by the group that is attached to the aromatic ring a priori. In this work, taking advantage of recent developments in quantifying nucleophilicity (electrophilicity) with descriptors from the information-theoretic approach in density functional reactivity theory, we examine the reactivity properties of this reaction system from three perspectives. These include scaling patterns of information-theoretic quantities such as Shannon entropy, Fisher information, Ghosh-Berkowitz-Parr entropy and information gain at both molecular and atomic levels, quantitative predictions of the barrier height with both Hirshfeld charge and information gain, and energetic decomposition analyses of the barrier height for the reactions. To that end, we focused in this work on the identity reaction of the monosubstituted-benzene molecule reacting with hydrogen fluoride using boron trifluoride as the catalyst in the gas phase. We also considered 19 substituting groups, 9 of which are ortho/para directing and the other 9 meta directing, besides the case of R = -H. Similar scaling patterns for these information-theoretic quantities found for stable species elsewhere were disclosed for these reactions systems. We also unveiled novel scaling patterns for information gain at the atomic level. The barrier height of the reactions can reliably be predicted by using both the Hirshfeld charge and information gain at the regioselective carbon atom. The energy decomposition analysis ensued yields an unambiguous picture about the origin of the barrier height, where we showed that it is the electrostatic interaction that plays the dominant role, while the roles played by exchange-correlation and

  1. Inorganic chemical composition and chemical reactivity of settled dust generated by the World Trade Center building collapse: Chapter 12

    Science.gov (United States)

    Plumlee, Geoffrey S.; Hageman, Philip L.; Lamothe, Paul J.; Ziegler, Thomas L.; Meeker, Gregory P.; Theodorakos, Peter M.; Brownfield, Isabelle; Adams, Monique G.; Swayze, Gregg A.; Hoefen, Todd M.; Taggart, Joseph E.; Clark, Roger N.; Wilson, S.; Sutley, Stephen J.

    2009-01-01

    Samples of dust deposited around lower Manhattan by the September 11, 2001, World Trade Center (WTC) collapse have inorganic chemical compositions that result in part from the variable chemical contributions of concrete, gypsum wallboard, glass fibers, window glass, and other materials contained in the buildings. The dust deposits were also modified chemically by variable interactions with rain water or water used in street washing and fire fighting. Chemical leach tests using deionized water as the extraction fluid show the dust samples can be quite alkaline, due primarily to reactions with calcium hydroxide in concrete particles. Calcium and sulfate are the most soluble components in the dust, but many other elements are also readily leached, including metals such as Al, Sb, Mo Cr, Cu, and Zn. Indoor dust samples produce leachates with higher pH, alkalinity, and dissolved solids than outdoor dust samples, suggesting most outdoor dust had reacted with water and atmospheric carbon dioxide prior to sample collection. Leach tests using simulated lung fluids as the extracting fluid suggest that the dust might also be quite reactive in fluids lining the respiratory tract, resulting in dissolution of some particles and possible precipitation of new phases such as phosphates, carbonates, and silicates. Results of these chemical characterization studies can be used by health scientists as they continue to track and interpret health effects resulting from the short-term exposure to the initial dust cloud and the longer-term exposure to dusts resuspended during cleanup.

  2. Reactive Imprint Lithography: Combined Topographical Patterning and Chemical Surface Functionalization of Polystyrene-block-poly(tert-butyl acrylate) Films

    NARCIS (Netherlands)

    Duvigneau, Joost; Cornelissen, Stijn; Bardajı´Valls, Nuria; Schönherr, Holger; Vancso, Gyula J.

    2009-01-01

    Here, reactive imprint lithography (RIL) is introduced as a new, one-step lithographic tool for the fabrication of large-area topographically patterned, chemically activated polymer platforms. Films of polystyrene-block-poly(tert-butyl acrylate) (PS-b-PtBA) are imprinted with PDMS master stamps at

  3. New chemical-DSMC method in numerical simulation of axisymmetric rarefied reactive flow

    Science.gov (United States)

    Zakeri, Ramin; Kamali Moghadam, Ramin; Mani, Mahmoud

    2017-04-01

    The modified quantum kinetic (MQK) chemical reaction model introduced by Zakeri et al. is developed for applicable cases in axisymmetric reactive rarefied gas flows using the direct simulation Monte Carlo (DSMC) method. Although, the MQK chemical model uses some modifications in the quantum kinetic (QK) method, it also employs the general soft sphere collision model and Stockmayer potential function to properly select the collision pairs in the DSMC algorithm and capture both the attraction and repulsion intermolecular forces in rarefied gas flows. For assessment of the presented model in the simulation of more complex and applicable reacting flows, first, the air dissociation is studied in a single cell for equilibrium and non-equilibrium conditions. The MQK results agree well with the analytical and experimental data and they accurately predict the characteristics of the rarefied flowfield with chemical reaction. To investigate accuracy of the MQK chemical model in the simulation of the axisymmetric flow, air dissociation is also assessed in an axial hypersonic flow around two geometries, the sphere as a benchmark case and the blunt body (STS-2) as an applicable test case. The computed results including the transient, rotational and vibrational temperatures, species concentration in the stagnation line, and also the heat flux and pressure coefficient on the surface are compared with those of the other chemical methods like the QK and total collision energy (TCE) models and available analytical and experimental data. Generally, the MQK chemical model properly simulates the chemical reactions and predicts flowfield characteristics more accurate rather than the typical QK model. Although in some cases, results of the MQK approaches match with those of the TCE method, the main point is that the MQK does not need any experimental data or unrealistic assumption of specular boundary condition as used in the TCE method. Another advantage of the MQK model is the

  4. Chemical Modeling of the Reactivity of Short-Lived Greenhouse Gases: A Model Inter-Comparison Prescribing a Well-Measured, Remote Troposphere

    Science.gov (United States)

    Prather, Michael J.; Flynn, Clare M.; Zhu, Xin; Steenrod, Stephen D.; Strode, Sarah A.; Fiore, Arlene M.; Correa, Gustavo; Murray, Lee T.; Lamarque, Jean-Francois

    2018-01-01

    We develop a new protocol for merging in situ measurements with 3-D model simulations of atmospheric chemistry with the goal of integrating over the data to identify the most reactive air parcels in terms of tropospheric production and loss of the greenhouse gases ozone and methane. Presupposing that we can accurately measure atmospheric composition, we examine whether models constrained by such measurements agree on the chemical budgets for ozone and methane. In applying our technique to a synthetic data stream of 14,880 parcels along 180W, we are able to isolate the performance of the photochemical modules operating within their global chemistry-climate and chemistry-transport models, removing the effects of modules controlling tracer transport, emissions, and scavenging. Differences in reactivity across models are driven only by the chemical mechanism and the diurnal cycle of photolysis rates, which are driven in turn by temperature, water vapor, solar zenith angle, clouds, and possibly aerosols and overhead ozone, which are calculated in each model. We evaluate six global models and identify their differences and similarities in simulating the chemistry through a range of innovative diagnostics. All models agree that the more highly reactive parcels dominate the chemistry (e.g., the hottest 10% of parcels control 25-30% of the total reactivities), but do not fully agree on which parcels comprise the top 10%. Distinct differences in specific features occur, including the regions of maximum ozone production and methane loss, as well as in the relationship between photolysis and these reactivities. Unique, possibly aberrant, features are identified for each model, providing a benchmark for photochemical module development. Among the 6 models tested here, 3 are almost indistinguishable based on the inherent variability caused by clouds, and thus we identify 4, effectively distinct, chemical models. Based on this work, we suggest that water vapor differences in

  5. Biodecolorization and biodegradation of Reactive Blue by ...

    African Journals Online (AJOL)

    SERVER

    2007-06-18

    Jun 18, 2007 ... Aspergillus sp. effectively decolorized Reactive Blue and other structurally different synthetic dyes. Agitation was found to be an important ... Few chemically different dyes such as Reactive Black (75%), Reactive Yellow (70%),. Reactive Red (33%) and ..... Degradation of azo dyes by the lignin degrading ...

  6. Chemical Identity of Interaction of Protein with Reactive Metabolite of Diosbulbin B In Vitro and In Vivo

    Directory of Open Access Journals (Sweden)

    Kai Wang

    2017-08-01

    Full Text Available Diosbulbin B (DIOB, a hepatotoxic furan-containing compound, is a primary ingredient in Dioscorea bulbifera L., a common herbal medicine. Metabolic activation is required for DIOB-induced liver injury. Protein covalent binding of an electrophilic reactive intermediate of DIOB is considered to be one of the key mechanisms of cytotoxicity. A bromine-based analytical technique was developed to characterize the chemical identity of interaction of protein with reactive intermediate of DIOB. Cysteine (Cys and lysine (Lys residues were found to react with the reactive intermediate to form three types of protein modification, including Cys adduction, Schiff’s base, and Cys/Lys crosslink. The crosslink showed time- and dose-dependence in animals given DIOB. Ketoconazole pretreatment decreased the formation of the crosslink derived from DIOB, whereas pretreatment with dexamethasone or buthionine sulfoximine increased such protein modification. These data revealed that the levels of hepatic protein adductions were proportional to the severity of hepatotoxicity of DIOB.

  7. THE INTEGRATED USE OF COMPUTATIONAL CHEMISTRY, SCANNING PROBE MICROSCOPY, AND VIRTUAL REALITY TO PREDICT THE CHEMICAL REACTIVITY OF ENVIRONMENTAL SURFACES

    Science.gov (United States)

    In the last decade three new techniques scanning probe microscopy (SPM), virtual reality (YR) and computational chemistry ave emerged with the combined capability of a priori predicting the chemically reactivity of environmental surfaces. Computational chemistry provides the cap...

  8. Substrate Vibrations as Promoters of Chemical Reactivity on Metal Surfaces.

    Science.gov (United States)

    Campbell, Victoria L; Chen, Nan; Guo, Han; Jackson, Bret; Utz, Arthur L

    2015-12-17

    Studies exploring how vibrational energy (Evib) promotes chemical reactivity most often focus on molecular reagents, leaving the role of substrate atom motion in heterogeneous interfacial chemistry underexplored. This combined theoretical and experimental study of methane dissociation on Ni(111) shows that lattice atom motion modulates the reaction barrier height during each surface atom's vibrational period, which leads to a strong variation in the reaction probability (S0) with surface temperature (Tsurf). State-resolved beam-surface scattering studies at Tsurf = 90 K show a sharp threshold in S0 at translational energy (Etrans) = 42 kJ/mol. When Etrans decreases from 42 kJ/mol to 34 kJ/mol, S0 decreases 1000-fold at Tsurf = 90 K, but only 2-fold at Tsurf = 475 K. Results highlight the mechanism for this effect, provide benchmarks for DFT calculations, and suggest the potential importance of surface atom induced barrier height modulation in heterogeneously catalyzed reactions, particularly on structurally labile nanoscale particles and defect sites.

  9. A theory for bioinorganic chemical reactivity of oxometal complexes and analogous oxidants: the exchange and orbital-selection rules.

    Science.gov (United States)

    Usharani, Dandamudi; Janardanan, Deepa; Li, Chunsen; Shaik, Sason

    2013-02-19

    Over the past decades metalloenzymes and their synthetic models have emerged as an area of increasing research interest. The metalloenzymes and their synthetic models oxidize organic molecules using oxometal complexes (OMCs), especially oxoiron(IV)-based ones. Theoretical studies have helped researchers to characterize the active species and to resolve mechanistic issues. This activity has generated massive amounts of data on the relationship between the reactivity of OMCs and the transition metal's identity, oxidation state, ligand sphere, and spin state. Theoretical studies have also produced information on transition state (TS) structures, reaction intermediates, barriers, and rate-equilibrium relationships. For example, the experimental-theoretical interplay has revealed that nonheme enzymes carry out H-abstraction from strong C-H bonds using high-spin (S = 2) oxoiron(IV) species with four unpaired electrons on the iron center. However, other reagents with higher spin states and more unpaired electrons on the metal are not as reactive. Still other reagents carry out these transformations using lower spin states with fewer unpaired electrons on the metal. The TS structures for these reactions exhibit structural selectivity depending on the reactive spin states. The barriers and thermodynamic driving forces of the reactions also depend on the spin state. H-Abstraction is preferred over the thermodynamically more favorable concerted insertion into C-H bonds. Currently, there is no unified theoretical framework that explains the totality of these fascinating trends. This Account aims to unify this rich chemistry and understand the role of unpaired electrons on chemical reactivity. We show that during an oxidative step the d-orbital block of the transition metal is enriched by one electron through proton-coupled electron transfer (PCET). That single electron elicits variable exchange interactions on the metal, which in turn depend critically on the number of

  10. Efficient modeling of reactive transport phenomena by a multispecies random walk coupled to chemical equilibrium

    International Nuclear Information System (INIS)

    Pfingsten, W.

    1996-01-01

    Safety assessments for radioactive waste repositories require a detailed knowledge of physical, chemical, hydrological, and geological processes for long time spans. In the past, individual models for hydraulics, transport, or geochemical processes were developed more or less separately to great sophistication for the individual processes. Such processes are especially important in the near field of a waste repository. Attempts have been made to couple at least two individual processes to get a more adequate description of geochemical systems. These models are called coupled codes; they couple predominantly a multicomponent transport model with a chemical reaction model. Here reactive transport is modeled by the sequentially coupled code MCOTAC that couples one-dimensional advective, dispersive, and diffusive transport with chemical equilibrium complexation and precipitation/dissolution reactions in a porous medium. Transport, described by a random walk of multispecies particles, and chemical equilibrium calculations are solved separately, coupled only by an exchange term. The modular-structured code was applied to incongruent dissolution of hydrated silicate gels, to movement of multiple solid front systems, and to an artificial, numerically difficult heterogeneous redox problem. These applications show promising features with respect to applicability to relevant problems and possibilities of extensions

  11. Fuels and chemicals from equine-waste-derived tail gas reactive pyrolysis oil: technoeconomic analysis, environmental and exergetic life cycle assessment

    Science.gov (United States)

    Horse manure, whose improper disposal imposes considerable environmental costs, constitutes an apt feedstock for conversion to renewable fuels and chemicals when tail gas reactive pyrolysis (TGRP) is employed. TGRP is a modification of fast pyrolysis that recycles its non-condensable gases and produ...

  12. Allergic contact dermatitis due to highly reactive halogenated compounds

    Energy Technology Data Exchange (ETDEWEB)

    Pickering, F C; Ive, F A

    1983-11-01

    Ten cases of dermatitis in a fine organic chemicals plant are reported. These cases were all due to exposure to chemical compounds with reactive bromine or chlorine atoms. This type of chemical is always extremely irritant, but evidence is put forward to suggest that these cases were the result of allergic sensitization. Chemicals with reactive halogen atoms should always be handled with extreme care and patch testing should be approached with caution.

  13. Assessing Chemical Transformation of Reactive, Interfacial Thin Films Made of End-Tethered Poly(2-vinyl-4,4-dimethyl azlactone) (PVDMA) Chains

    Energy Technology Data Exchange (ETDEWEB)

    Aden, Bethany [Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemistry; Kite, Camille M. [Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemistry; Hopkins, Benjamin W. [Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemical and Biomolecular Engineering; Zetterberg, Anna [Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemical and Biomolecular Engineering; Lokitz, Bradley S. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science (CNMS); Ankner, John Francis [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Spallation Neutron Source (SNS); Kilbey, S. Michael [Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemistry; Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemical and Biomolecular Engineering

    2017-01-24

    Designing thin films or surface scaffolds with an appropriate display of chemical functionality is useful for biomedical applications, sensing platforms, adhesives, and barrier coatings. Relationships between the structural characteristics of model thin films based on reactive poly(2-vinyl-4,4-dimethylazlactone) (PVDMA) brushes and the amount and distribution of primary amines used to chemically functionalize the layer in situ are quantitatively detailed via neutron reflectometry and compared with results from ellipsometry. After functionalization, the PVDMA brush thickness increases as a result of the primary amines reacting with the azlactone rings. Both techniques show that the extent of functionalization by small-molecule amines depends on the size of the amine, the grafting density of brush chains and their molecular weight. However, constrained analysis of neutron reflectivity data predicated on that technique’s sensitivity to isotopic substitution and its ability to resolve structure at the nanoscale, shows that the extent of functionalization is not accurately represented by the average extent of functionalization determined from ellipsometric thickness: reactive modification is not uniform, even in modestly dense brushes, except when the penetrant is small. Additionally, there appears to be a loss of PVDMA chains during functionalization, attributed to chain scission resulting from additional stretching brought about by functionalization. These findings provide unprecedented insight into the alteration of surface properties by reactive modification and broadly support efforts to produce tailored surfaces in which properties such as friction, colloidal stability, adhesion, wettability, and biocompatibility can be modulated in situ by chemical modification.

  14. Methyl salicylate: a reactive chemical warfare agent surrogate to detect reaction with hypochlorite.

    Science.gov (United States)

    Salter, W Bruce; Owens, Jeffery R; Wander, Joseph D

    2011-11-01

    Methyl salicylate (MeS) has a rich history as an inert physical simulant for the chemical warfare agents sulfur mustard and soman, where it is used extensively for liquid- and vapor-permeation testing. Here we demonstrate possible utility of MeS as a reactivity simulant for chlorine-based decontaminants. In these experiments MeS was reacted with sodium hypochlorite varying stoichiometry, temperature, reaction time, and pH. No colored oxidation products were observed; however, chlorination of the aromatic ring occurred ortho (methyl 3-chlorosalicylate) and para (methyl 5-chlorosalicylate) to the position bearing the -OH group in both the mono- and disubstituted forms. The monosubstituted para product accumulated initially, and the ortho and 3,5-dichloro products formed over the next several hours. Yields from reactions conducted below pH 11 declined rapidly with decreasing pH. Reactions run at 40 °C produced predominantly para substitution, while those run at 0 °C produced lower yields of ortho- and para-substituted products. Reactions were also carried out on textile substrates of cotton, 50/50 nylon-cotton, and a meta aramid. The textile data broadly reproduced reaction times and stoichiometry observed in the liquid phase, but are complicated by physical and possibly chemical interactions with the fabric. These data indicate that, for hypochlorite-containing neutralizing agents operating at strongly alkaline pH, one can expect MeS to react stoichiometrically with the hypochlorite it encounters. This suggests utility of MeS in lieu of such highly hazardous surrogates as monochloroalkyl sulfides as a simulant for threat scenarios involving the stoichiometric decomposition of sulfur mustard. Specifically, the extent of coverage of the simulant on a fabric by the neutralizing agent can be directly measured. Similar reactivity toward other halogen oxidizing agents is likely but remains to be demonstrated.

  15. Journal of Chemical Sciences | Indian Academy of Sciences

    Indian Academy of Sciences (India)

    DFT global chemical reactivity descriptors (chemical hardness, total energy, electronic chemical potential, and electrophilicity) are calculated for the isomers and used to predict their relative stability and reactivity. The chemical reactivity indices are found to be related to the bond angle defined by the cis carbonyls and the ...

  16. Chemical reactor modeling multiphase reactive flows

    CERN Document Server

    Jakobsen, Hugo A

    2014-01-01

    Chemical Reactor Modeling closes the gap between Chemical Reaction Engineering and Fluid Mechanics.  The second edition consists of two volumes: Volume 1: Fundamentals. Volume 2: Chemical Engineering Applications In volume 1 most of the fundamental theory is presented. A few numerical model simulation application examples are given to elucidate the link between theory and applications. In volume 2 the chemical reactor equipment to be modeled are described. Several engineering models are introduced and discussed. A survey of the frequently used numerical methods, algorithms and schemes is provided. A few practical engineering applications of the modeling tools are presented and discussed. The working principles of several experimental techniques employed in order to get data for model validation are outlined. The monograph is based on lectures regularly taught in the fourth and fifth years graduate courses in transport phenomena and chemical reactor modeling, and in a post graduate course in modern reactor m...

  17. How well can global chemistry models calculate the reactivity of short-lived greenhouse gases in the remote troposphere, knowing the chemical composition

    Science.gov (United States)

    Prather, Michael J.; Flynn, Clare M.; Zhu, Xin; Steenrod, Stephen D.; Strode, Sarah A.; Fiore, Arlene M.; Correa, Gustavo; Murray, Lee T.; Lamarque, Jean-Francois

    2018-05-01

    We develop a new protocol for merging in situ measurements with 3-D model simulations of atmospheric chemistry with the goal of integrating these data to identify the most reactive air parcels in terms of tropospheric production and loss of the greenhouse gases ozone and methane. Presupposing that we can accurately measure atmospheric composition, we examine whether models constrained by such measurements agree on the chemical budgets for ozone and methane. In applying our technique to a synthetic data stream of 14 880 parcels along 180° W, we are able to isolate the performance of the photochemical modules operating within their global chemistry-climate and chemistry-transport models, removing the effects of modules controlling tracer transport, emissions, and scavenging. Differences in reactivity across models are driven only by the chemical mechanism and the diurnal cycle of photolysis rates, which are driven in turn by temperature, water vapor, solar zenith angle, clouds, and possibly aerosols and overhead ozone, which are calculated in each model. We evaluate six global models and identify their differences and similarities in simulating the chemistry through a range of innovative diagnostics. All models agree that the more highly reactive parcels dominate the chemistry (e.g., the hottest 10 % of parcels control 25-30 % of the total reactivities), but do not fully agree on which parcels comprise the top 10 %. Distinct differences in specific features occur, including the spatial regions of maximum ozone production and methane loss, as well as in the relationship between photolysis and these reactivities. Unique, possibly aberrant, features are identified for each model, providing a benchmark for photochemical module development. Among the six models tested here, three are almost indistinguishable based on the inherent variability caused by clouds, and thus we identify four, effectively distinct, chemical models. Based on this work, we suggest that water vapor

  18. The influence of condensed tannin structure on rate of microbial mineralization and reactivity to chemical assays.

    Science.gov (United States)

    Norris, Charlotte E; Preston, Caroline M; Hogg, Karen E; Titus, Brian D

    2011-03-01

    We examined how tannin structure influences reactivity in tannin assays and carbon and nitrogen mineralization. Condensed tannins from the foliage of ten tree and shrub species and from pecan shells (Carya illinoensis) had different proportions of: (a) epicatechin (cis) and catechin (trans) isomers, (b) procyanidin (PC) and prodelphinidin (PD) monomers, and (c) different chain lengths. The response of each tannin to several widely used tannin assays was determined. Although there was some variation in response to proanthocyanidin (butanol/HCl) and Folin Ciocalteu assays, we did not deduce any predictable relationship between tannin structure and response to either assay. There was little variation in protein precipitation among the different tannins. To assess biological activity, six of the tannins were incubated with forest humus for 22 days. We determined that, while PC-based tannins remained at least partly extractable for the duration of the incubation, tannins with a high proportion of PD subunits rapidly became unextractable from soil. There was a positive correlation between net nitrogen mineralization and cis chemical structure. Carbon mineralization was enhanced initially by the addition of tannins to humus, but after 22 days, a negative correlation between the proportion of cis subunits and respiration was determined. Overall, we were not able to demonstrate consistent effects of structure on either microbial mineralization or reactivity to chemical assays; such relationships remain elusive.

  19. Reactivity of polychlorinated biphenyls in nucleophilic and electrophilic substitutions

    Energy Technology Data Exchange (ETDEWEB)

    Gorbunova, Tatyana I., E-mail: gorbunova@ios.uran.ru [I. Ya. Postovskii Institute of Organic Synthesis, Ural Branch, Russian Academy of Sciences, Kovalevskoy St., 22, Ekaterinburg 620990 (Russian Federation); Subbotina, Julia O. [Ural Federal University named after the first President of Russia B.N. Yeltsin, Mira St., 19, Ekaterinburg 620002 (Russian Federation); Saloutin, Viktor I.; Chupakhin, Oleg N. [I. Ya. Postovskii Institute of Organic Synthesis, Ural Branch, Russian Academy of Sciences, Kovalevskoy St., 22, Ekaterinburg 620990 (Russian Federation)

    2014-08-15

    Graphical abstract: - Highlights: • Quantum chemical calculations were carried out for PCBs congeners. • Calculated descriptors were used to explain the PCBs reactivity in S{sub N} and S{sub E} substitutions. • Obtained data were used to estimate the PCBs reactivity in the S{sub N} reactions. • Calculated descriptors were insufficient to explain the PCBs reactivity in the S{sub E} reactions. • New neutralization methods of the large-capacity PCBs were discussed. - Abstract: To explain the chemical reactivity of polychlorinated biphenyls in nucleophilic (S{sub N}) and electrophilic (S{sub E}) substitutions, quantum chemical calculations were carried out at the B3LYP/6-31G(d) level of the Density Functional Theory in gas phase. Carbon atomic charges in biphenyl structure were calculated by the Atoms-in-Molecules method. Chemical hardness and global electrophilicity index parameters were determined for congeners. A comparison of calculated descriptors and experimental data for congener reactivity in the S{sub N} and S{sub E} reactions was made. It is shown that interactions in the S{sub N} mechanism are reactions of the hard acid–hard base type, these are the most effective in case of highly chlorinated substrates. To explain the congener reactivity in the S{sub E} reactions, correct descriptors were not established. The obtained results can be used to carry out chemical transformations of the polychlorinated biphenyls in order to prepare them for microbiological destruction or preservation.

  20. Chemical Reactivity Testing for the National Spent Nuclear Fuel Program. Quality Assurance Project Plan

    International Nuclear Information System (INIS)

    Newsom, H.C.

    1999-01-01

    This quality assurance project plan (QAPjP) summarizes requirements used by Lockheed Martin Energy Systems, Incorporated (LMES) Development Division at Y-12 for conducting chemical reactivity testing of Department of Energy (DOE) owned spent nuclear fuel, sponsored by the National Spent Nuclear Fuel Program (NSNFP). The requirements are based on the NSNFP Statement of Work PRO-007 (Statement of Work for Laboratory Determination of Uranium Hydride Oxidation Reaction Kinetics.) This QAPjP will utilize the quality assurance program at Y-12, QA-101PD, revision 1, and existing implementing procedures for the most part in meeting the NSNFP Statement of Work PRO-007 requirements, exceptions will be noted

  1. Unravelling chemical priming machinery in plants: the role of reactive oxygen-nitrogen-sulfur species in abiotic stress tolerance enhancement.

    Science.gov (United States)

    Antoniou, Chrystalla; Savvides, Andreas; Christou, Anastasis; Fotopoulos, Vasileios

    2016-10-01

    Abiotic stresses severely limit crop yield and their detrimental effects are aggravated by climate change. Chemical priming is an emerging field in crop stress management. The exogenous application of specific chemical agents before stress events results in tolerance enhancement and reduction of stress impacts on plant physiology and growth. However, the molecular mechanisms underlying the remarkable effects of chemical priming on plant physiology remain to be elucidated. Reactive oxygen, nitrogen and sulfur species (RONSS) are molecules playing a vital role in the stress acclimation of plants. When applied as priming agents, RONSS improve stress tolerance. This review summarizes the recent knowledge on the role of RONSS in cell signalling and gene regulation contributing to abiotic stress tolerance enhancement. Copyright © 2016 Elsevier Ltd. All rights reserved.

  2. Reactive sites influence in PMMA oligomers reactivity: a DFT study

    Science.gov (United States)

    Paz, C. V.; Vásquez, S. R.; Flores, N.; García, L.; Rico, J. L.

    2018-01-01

    In this work, we present a theoretical study of methyl methacrylate (MMA) living anionic polymerization. The study was addressed to understanding two important experimental observations made for Michael Szwarc in 1956. The unexpected effect of reactive sites concentration in the propagation rate, and the self-killer behavior of MMA (deactivating of living anionic polymerization). The theoretical calculations were performed by density functional theory (DFT) to obtain the frontier molecular orbitals values. These values were used to calculate and analyze the chemical interaction descriptors in DFT-Koopmans’ theorem. As a result, it was observed that the longest chain-length species (related with low concentration of reactive sites) exhibit the highest reactivity (behavior associated with the increase of the propagation rate). The improvement in this reactivity was attributed to the crosslinking produced in the polymethyl methacrylate chains. Meanwhile, the self-killer behavior was associated with the intermolecular forces present in the reactive sites. This behavior was associated to an obstruction in solvation, since the active sites remained active through all propagation species. The theoretical results were in good agreement with the Szwarc experiments.

  3. The chemical reactivity of the Martian soil and implications for future missions

    Science.gov (United States)

    Zent, Aaron P.; Mckay, Christopher P.

    1994-01-01

    Possible interpretations of the results of the Viking Biology Experiments suggest that greater than 1 ppm of a thermally labile oxidant, perhaps H2O2, and about 10 ppm of a thermally stable oxidant are present in the martian soil. We reexamine these results and discuss implications for future missions, the search for organics on Mars, and the possible health and engineering effects for human exploration. We conclude that further characterization of the reactivity of the martian regolith materials is warrented-although if our present understanding is correct the oxidant does not pose a hazard to humans. There are difficulties in explaining the reactivity of the Martian soil by oxidants. Most bulk phase compounds that are capable of oxidizing H2O to O2 per the Gas Exchange Experiment (GEx) are thermally labile or unstable against reduction by atmospheric CO2. Models invoking trapped O2 or peroxynitrates (NOO2(-)) require an unlikely geologic history for the Viking Lander 2 site. Most suggested oxidants, including H2O2, are expected to decompose rapidly under martian UV. Nonetheless, we conclude that the best model for the martian soil contains oxidants produced by heterogeneous chemical reactions with a photochemically produced atmospheric oxidant. The GEx results may be due to catalytic decomposition of an unstable oxidizing material by H2O. We show that interfacial reaction sites covering less than 1% of the available soil surfaces could explain the Viking Biology Experiments results.

  4. The reactive metabolite target protein database (TPDB)--a web-accessible resource.

    Science.gov (United States)

    Hanzlik, Robert P; Koen, Yakov M; Theertham, Bhargav; Dong, Yinghua; Fang, Jianwen

    2007-03-16

    The toxic effects of many simple organic compounds stem from their biotransformation to chemically reactive metabolites which bind covalently to cellular proteins. To understand the mechanisms of cytotoxic responses it may be important to know which proteins become adducted and whether some may be common targets of multiple toxins. The literature of this field is widely scattered but expanding rapidly, suggesting the need for a comprehensive, searchable database of reactive metabolite target proteins. The Reactive Metabolite Target Protein Database (TPDB) is a comprehensive, curated, searchable, documented compilation of publicly available information on the protein targets of reactive metabolites of 18 well-studied chemicals and drugs of known toxicity. TPDB software enables i) string searches for author names and proteins names/synonyms, ii) more complex searches by selecting chemical compound, animal species, target tissue and protein names/synonyms from pull-down menus, and iii) commonality searches over multiple chemicals. Tabulated search results provide information, references and links to other databases. The TPDB is a unique on-line compilation of information on the covalent modification of cellular proteins by reactive metabolites of chemicals and drugs. Its comprehensiveness and searchability should facilitate the elucidation of mechanisms of reactive metabolite toxicity. The database is freely available at http://tpdb.medchem.ku.edu/tpdb.html.

  5. 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.

  6. 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.

  7. Local and linear chemical reactivity response functions at finite temperature in density functional theory

    International Nuclear Information System (INIS)

    Franco-Pérez, Marco; Ayers, Paul W.; Gázquez, José L.; Vela, Alberto

    2015-01-01

    We explore the local and nonlocal response functions of the grand canonical potential density functional at nonzero temperature. In analogy to the zero-temperature treatment, local (e.g., the average electron density and the local softness) and nonlocal (e.g., the softness kernel) intrinsic response functions are defined as partial derivatives of the grand canonical potential with respect to its thermodynamic variables (i.e., the chemical potential of the electron reservoir and the external potential generated by the atomic nuclei). To define the local and nonlocal response functions of the electron density (e.g., the Fukui function, the linear density response function, and the dual descriptor), we differentiate with respect to the average electron number and the external potential. The well-known mathematical relationships between the intrinsic response functions and the electron-density responses are generalized to nonzero temperature, and we prove that in the zero-temperature limit, our results recover well-known identities from the density functional theory of chemical reactivity. Specific working equations and numerical results are provided for the 3-state ensemble model

  8. Study of a new hybrid process combining slurry infiltration and Reactive Chemical Vapour Infiltration for the realisation of Ceramic Matrix Composites

    International Nuclear Information System (INIS)

    Ledain, Olivier

    2014-01-01

    Ceramic matrix composites were originally developed for aerospace,military aeronautics or energy applications thanks to their good properties at high temperature. They are generally made by Chemical Vapor Infiltration (CVI). A new short hybrid process combining fiber preform slurry impregnation of ceramic powders with an innovative Reactive CVI (RCVI) route is proposed to reduce the production time. This route is based on the combination of Reactive Chemical Vapour Deposition (RCVD), which is often used to deposit coatings on fibres, with the Chemical Vapor Infiltration (CVI).In RCVD, the absence of one element of the deposited carbide in the initial gas phase involves the consumption/conversion of the solid substrate. In this work, the RCVD growth and the associated consumption were studied with different parameters in the Ti-H-Cl-C chemical system. The study has been completed with the chemical products analysis, combining XRD, XPS and FTIR. Then, the partial conversion of sub-micrometer carbon powders into titanium carbide and the consolidation of green bodies by RCVI from H 2 /TiCl 4 gaseous infiltration were studied. The residual porosity and the final TiC content were measured in the bulk of the infiltrated powders by image analysis from scanning electron microscopy. Depending on temperature, few hundred micrometers-depth infiltrations are obtained.Finally, the results have been transposed to the RCVI into CMC-type pre-forms. Despite a minimal TiC content of 25% in the overall preform, the results shown a bad homogeneity of the infiltration and a poor cohesion of fibres with RCVI consolidated powder of their environment. (author) [fr

  9. 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 ...

  10. How well can global chemistry models calculate the reactivity of short-lived greenhouse gases in the remote troposphere, knowing the chemical composition

    Directory of Open Access Journals (Sweden)

    M. J. Prather

    2018-05-01

    Full Text Available We develop a new protocol for merging in situ measurements with 3-D model simulations of atmospheric chemistry with the goal of integrating these data to identify the most reactive air parcels in terms of tropospheric production and loss of the greenhouse gases ozone and methane. Presupposing that we can accurately measure atmospheric composition, we examine whether models constrained by such measurements agree on the chemical budgets for ozone and methane. In applying our technique to a synthetic data stream of 14 880 parcels along 180° W, we are able to isolate the performance of the photochemical modules operating within their global chemistry-climate and chemistry-transport models, removing the effects of modules controlling tracer transport, emissions, and scavenging. Differences in reactivity across models are driven only by the chemical mechanism and the diurnal cycle of photolysis rates, which are driven in turn by temperature, water vapor, solar zenith angle, clouds, and possibly aerosols and overhead ozone, which are calculated in each model. We evaluate six global models and identify their differences and similarities in simulating the chemistry through a range of innovative diagnostics. All models agree that the more highly reactive parcels dominate the chemistry (e.g., the hottest 10 % of parcels control 25–30 % of the total reactivities, but do not fully agree on which parcels comprise the top 10 %. Distinct differences in specific features occur, including the spatial regions of maximum ozone production and methane loss, as well as in the relationship between photolysis and these reactivities. Unique, possibly aberrant, features are identified for each model, providing a benchmark for photochemical module development. Among the six models tested here, three are almost indistinguishable based on the inherent variability caused by clouds, and thus we identify four, effectively distinct, chemical models. Based on this

  11. The surface chemical reactivity of particles and its impact on human health

    Science.gov (United States)

    Setyan, A.; Sauvain, J. J.; Riediker, M.; Guillemin, M.; Rossi, M. J.

    2017-12-01

    The chemical composition of the particle-air interface is the gateway to chemical reactions of gases with condensed phase particles. It is of prime importance to understand the reactivity of particles and their interaction with surrounding gases, biological membranes, and solid supports. We used a Knudsen flow reactor to quantify functional groups on the surface of a few selected particle types. This technique is based on a heterogeneous titration reaction between a probe gas and a specific functional group on the particle surface. Six probe gases have been selected for the identification and quantification of important functional groups: N(CH3)3 for the titration of acidic sites, NH2OH for the detection of carbonyl functions (aldehydes and ketones) and/or oxidized sites owing to its strong reducing properties, CF3COOH and HCl for basic sites of different strength, O3 and NO2 for oxidizable groups. We also studied the kinetics of the reactions between particles and probe gases (uptake coefficient γ0). We tested the surface chemical composition and oxidation states of laboratory-generated aerosols (3 amorphous carbons, 2 flame soots, 2 Diesel particles, 2 secondary organic aerosols [SOA], 4 multiwall carbon nanotubes [MWCNT], 3 TiO2, and 2 metal salts) and of aerosols sampled in several bus depots. The sampling of particles in the bus depots was accompanied by the collection of urine samples of mechanics working full-time in these bus depots, and the quantification of 8-hydroxy-2'-deoxyguanosine, a biomarker of oxidative stress. The increase in oxidative stress biomarker levels over a working day was correlated (pcellular antioxidants.

  12. The Atmospheric Tomography Mission (ATom): Comparing the Chemical Climatology of Reactive Species and Air Parcels from Measurements and Global Models

    Science.gov (United States)

    Prather, M. J.; Flynn, C.; Wennberg, P. O.; Kim, M. J.; Ryerson, T. B.; Hanisco, T. F.; Diskin, G. S.; Daube, B. C.; Commane, R.; McKain, K.; Apel, E. C.; Blake, N. J.; Blake, D. R.; Elkins, J. W.; Hall, S.; Steenrod, S.; Strahan, S. E.; Lamarque, J. F.; Fiore, A. M.; Horowitz, L. W.; Murray, L. T.; Mao, J.; Shindell, D. T.; Wofsy, S. C.

    2017-12-01

    The NASA Atmospheric Tomography Mission (ATom) is building a photochemical climatology of the remote troposphere based on objective sampling and profiling transects over the Pacific and Atlantic Oceans. These statistics provide direct tests of chemistry-climate models. The choice of species focuses on those controlling primary reactivity (a.k.a. oxidative state) of the troposphere, specifically chemical tendencies of O3 and CH4. These key species include, inter alia, O3, CH4, CO, C2H6, other alkanes, alkenes, aromatics, NOx, HNO3, HO2NO2, PAN, other organic nitrates, H2O, HCHO, H2O2, CH3OOH. Three of the four ATom deployments are now complete, and data from the first two (ATom-1 & -2) have been released as of this talk (see espoarchive.nasa.gov/archive/browse/atom). The statistical distributions of key species are presented as 1D and 2D probability densities (PDs) and we focus here on the tropical and mid-latitude regions of the Pacific during ATom-1 (Aug) and -2 (Feb). PDs are computed from ATom observations and 6 global chemistry models over the tropospheric depth (0-12 km) and longitudinal extent of the observations. All data are weighted to achieve equal mass-weighting by latitude regimes to account for spatial sampling biases. The models are used to calculate the reactivity in each ATom air parcel. Reweighting parcels with loss of CH4 or production of O3, for example, allows us to identify which air parcels are most influential, including assessment of the importance of fine pollution layers in the most remote troposphere. Another photochemical climatology developed from ATom, and used to test models, includes the effect of clouds on photolysis rates. The PDs and reactivity-weighted PDs reveal important seasonal differences and similarities between the two campaigns and also show which species may be most important in controlling reactivities. They clearly identify some very specific failings in the modeled climatologies and help us evaluate the chemical

  13. From Chemical Forces to Chemical Rates: A Historical/Philosophical Foundation for the Teaching of Chemical Equilibrium

    Science.gov (United States)

    Quilez, Juan

    2009-01-01

    With this paper, our main aim is to contribute to the realisation of the chemical reactivity concept, tracing the historical evolution of the concept of chemical affinity that eventually supported the concept of chemical equilibrium. We will concentrate on searching for the theoretical grounds of three key chemical equilibrium ideas: "incomplete…

  14. Adsorption of a reactive dye on chemically modified activated carbons--influence of pH.

    Science.gov (United States)

    Orfão, J J M; Silva, A I M; Pereira, J C V; Barata, S A; Fonseca, I M; Faria, P C C; Pereira, M F R

    2006-04-15

    The surface chemistry of a commercial activated carbon with a slightly basic nature was modified by appropriate treatments in order to obtain two additional samples, respectively with acidic and basic properties, without changing its textural parameters significantly. Different techniques (N2 adsorption at 77 K, temperature programmed desorption, and determination of acidity, basicity, and pH at the point of zero charge) were used to characterize the adsorbents. Kinetic and equilibrium adsorption data of a selected textile reactive dye (Rifafix Red 3BN, C.I. reactive red 241) on the mentioned materials were obtained at the pH values of 2, 7, and 12. The kinetic curves are fitted using the second-order model. The respective rate constants seem to diminish progressively with the initial concentration for the more diluted solutions tested, reaching a constant value at higher concentrations, which depends on the experimental system under consideration (adsorbent and pH). In general, the Langmuir model provides the best fit for the equilibrium data. The different uptakes obtained are discussed in relation to the surface chemical properties of the adsorbents. It is shown that the adsorption of the reactive (anionic) dye on the basic sample (prepared by thermal treatment under H2 flow at 700 degrees C) is favored. This conclusion is explained on the basis of the dispersive and electrostatic interactions involved. Moreover, it is also shown that the optimal adsorption condition for all the activated carbons tested corresponds to solution pH values not higher than the pH(pzc) of the adsorbents, which may be interpreted by taking into account the electrostatic forces present.

  15. Topological analysis (BCP) of vibrational spectroscopic studies, docking, RDG, DSSC, Fukui functions and chemical reactivity of 2-methylphenylacetic acid

    Science.gov (United States)

    Kavimani, M.; Balachandran, V.; Narayana, B.; Vanasundari, K.; Revathi, B.

    2018-02-01

    Experimental FT-IR and FT-Raman spectra of 2-methylphenylacetic acid (MPA) were recorded and theoretical values are also analyzed. The non-linear optical (NLO) properties were evaluated by determination of first (5.5053 × 10- 30 e.s.u.) and second hyper-polarizabilities (7.6833 × 10- 36 e.s.u.) of the title compound. The Multiwfn package is used to find the weak non-covalent interaction (Van der Wall interaction) and strong repulsion (steric effect) of the molecule and examined by reduced density gradient. The molecular electrostatic potential (MEP) analysis used to find the most reactive sites for the electrophilic and nucleophilic attack. The chemical activity (electronegativity, hardness, chemical softness and chemical potential) of the title compound was predicted with the help of HOMO-LUMO energy values. The natural bond orbital (NBO) has been analyzed the stability of the molecule arising from the hyper-conjugative interaction. DSSCs were discussed in structural modifications that improve the electron injection efficiency of the title compound (MPA). The Fukui functions are calculated in order to get information associated with the local reactivity properties of the title compound. The binding sites of the two receptors were reported by molecular docking field and active site bond distance is same 1.9 Å. The inhibitor of the title compound forms a stable complex with 1QYV and 2H1K proteins at the binding energies are - 5.38 and - 5.85 (Δ G in kcal/mol).

  16. 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.

  17. Reactive hydro- end chlorocarbons in the troposphere and lower stratosphere : sources, distributions, and chemical impact

    Science.gov (United States)

    Scheeren, H. A.

    2003-09-01

    The work presented in this thesis focuses on measurements of chemical reactive C2 C7 non-methane hydrocarbons (NMHC) and C1 C2 chlorocarbons with atmospheric lifetimes of a few hours up to about a year. The group of reactive chlorocarbons includes the most abundant atmospheric species with large natural sources, which are chloromethane (CH3Cl), dichloromethane (CH2Cl2), and trichloromethane (CHCl3), and tetrachloroethylene (C2Cl4) with mainly anthropogenic sources. The NMHC and chlorocarbons are present at relatively low quantities in our atmosphere (10-12 10-9 mol mol-1 of air). Nevertheless, they play a key role in atmospheric photochemistry. For example, the oxidation of NMHC plays a dominant role in the formation of ozone in the troposphere, while the photolysis of chlorocarbons contributes to enhanced ozone depletion in the stratosphere. In spite of their important role, however, their global source and sinks budgets are still poorly understood. Hence, this study aims at improving our understanding of the sources, distribution, and chemical role of reactive NMHC and chlorocarbons in the troposphere and lower stratosphere. To meet this aim, a comprehensive data set of selected C2 C7 NMHC and chlorocarbons has been analyzed, derived from six aircraft measurement campaigns with two different jet aircrafts (the Dutch TUD/NLR Cessna Citation PH-LAB, and the German DLR Falcon) conducted between 1995 and 2001 (STREAM 1995 and 1997 and 1998, LBA-CLAIRE 1998, INDOEX 1999, MINOS 2001). The NMHC and chlorocarbons have been detected by gas-chromatography (GC-FID/ECD) in pre-concentrated whole air samples collected in stainless steel canister on-board the measurement aircrafts. The measurement locations include tropical (Maldives/Indian Ocean and Surinam), midlatitude (Western Europe and Canada) and polar regions (Lapland/northern Sweden) between the equator to about 70ºN, covering different seasons and pollution levels in the troposphere and lower stratosphere. Of

  18. Structure, reactivity, and biological properties of hidantoines

    International Nuclear Information System (INIS)

    Oliveira, Silvania Maria de; Silva, Joao Bosco Paraiso da; Hernandes, Marcelo Zaldini; Lima, Maria do Carmo Alves de; Galdino, Suely Lins; Pitta, Ivan da Rocha

    2008-01-01

    Hydantoin (imidazolidine-2,4-dione) is a 2,4-diketotetrahydroimidazole discovered by Baeyer in 1861. Thiohydantoins and derivatives were prepared, having chemical properties similar to the corresponding carbonyl compounds. Some biological activities (antimicrobial, anticonvulsant, schistosomicidal) are attributed to the chemical reactivity and consequent affinity of hydantoinic rings towards biomacromolecules. Therefore, knowledge about the chemistry of hydantoins has increased enormously. In this review, we present important aspects such as reactivity of hydantoins, acidity of hydantoins, spectroscopy and crystallographic properties, and biological activities of hydantoin and its derivatives. (author)

  19. Simulations of the dispersion of reactive pollutants in a street canyon, considering different chemical mechanisms and micromixing

    Science.gov (United States)

    Garmory, A.; Kim, I. S.; Britter, R. E.; Mastorakos, E.

    The Stochastic Fields (SF) or Field Monte Carlo method has been used to model the dispersion of reactive scalars in a street canyon, using a simple chemistry and the CBM-IV mechanism. SF is a Probability Density Function (PDF) method which allows both means and variances of the scalars to be calculated as well as considering the effect of segregation on reaction rates. It was found that the variance of reactive scalars such as NO 2 was very high in the mixing region at roof-top level with rms values of the order of the mean values. The effect of segregation on major species such as O 3 was found to be very small using either mechanism, however, some radical species in CBM-IV showed a significant difference. These were found to be the seven species with the fastest chemical timescales. The calculated photostationary state defect was also found to be in error when segregation is neglected.

  20. Vibrational deactivation on chemically reactive potential surfaces: An exact quantum study of a low barrier collinear model of H + FH, D + FD, H + FD and D + FH

    International Nuclear Information System (INIS)

    Schatz, G.C.; Kuppermann, A.

    1980-01-01

    We study vibrational deactivation processes on chemically reactive potential energy surfaces by examining accurate quantum mechanical transition probabilities and rate constants for the collinear H + FH(v), D + FD(v), H + FD(v), and D + FH(v) reactions. A low barrier (1.7 kcal/mole) potential surface is used in these calculations, and we find that for all four reactions, the reactive inelastic rate constants are larger than the nonreactive ones for the same initial and final vibrational states. However, the ratios of these reactive and nonreactive rate constants depend strongly on the vibrational quantum number v and the isotopic composition of the reagents. Nonreactive and reactive transition probabilities for multiquantum jump transitions are generally comparable to those for single quantum transitions. This vibrationally nonadiabatic behavior is a direct consequence of the severe distortion of the diatomic that occurs in a collision on a low barrier reactive surface, and can make chemically reactive atoms like H or D more efficient deactivators of HF or DF than nonreactive collision partners. Many conclusions are in at least qualitative agreement with those of Wilkin's three dimensional quasiclassical trajectory study on the same systems using a similar surface. We also present results for H + HF(v) collisions which show that for a higher barrier potential surface (33 rather than 1.7 kcal/mole), the deactivation process becomes similar in character to that for nonreactive partners, with v→v-1 processes dominating

  1. Termination of nanoscale zero-valent iron reactivity by addition of bromate as a reducing reactivity competitor

    Science.gov (United States)

    Mines, Paul D.; Kaarsholm, Kamilla M. S.; Droumpali, Ariadni; Andersen, Henrik R.; Lee, Wontae; Hwang, Yuhoon

    2017-09-01

    Remediation of contaminated groundwater by nanoscale zero-valent iron (nZVI) is widely becoming a leading environmentally friendly solution throughout the globe. Since a wide range of various nZVI-containing materials have been developed for effective remediation, it is necessary to determine an appropriate way to terminate the reactivity of any nZVI-containing material for a practical experimental procedure. In this study, bimetallic Ni/Fe-NPs were prepared to enhance overall reduction kinetics owing to the catalytic reactivity of nickel on the surface of nZVI. We have tested several chemical strategies in order to terminate nZVI reactivity without altering the concentration of volatile compounds in the solution. The strategies include surface passivation in alkaline conditions by addition of carbonate, and consumption of nZVI by a reaction competitor. Four halogenated chemicals, trichloroethylene, 1,1,1-trichloroethane, atrazine, and 4-chlorophenol, were selected and tested as model groundwater contaminants. Addition of carbonate to passivate the nZVI surface was not effective for trichloroethylene. Nitrate and then bromate were applied to competitively consume nZVI by their faster reduction kinetics. Bromate proved to be more effective than nitrate, subsequently terminating nZVI reactivity for all four of the tested halogenated compounds. Furthermore, the suggested termination method using bromate was successfully applied to obtain trichloroethylene reduction kinetics. Herein, we report the simple and effective method to terminate the reactivity of nZVI by addition of a reducing reactivity competitor.

  2. The reactive metabolite target protein database (TPDB – a web-accessible resource

    Directory of Open Access Journals (Sweden)

    Dong Yinghua

    2007-03-01

    Full Text Available Abstract Background The toxic effects of many simple organic compounds stem from their biotransformation to chemically reactive metabolites which bind covalently to cellular proteins. To understand the mechanisms of cytotoxic responses it may be important to know which proteins become adducted and whether some may be common targets of multiple toxins. The literature of this field is widely scattered but expanding rapidly, suggesting the need for a comprehensive, searchable database of reactive metabolite target proteins. Description The Reactive Metabolite Target Protein Database (TPDB is a comprehensive, curated, searchable, documented compilation of publicly available information on the protein targets of reactive metabolites of 18 well-studied chemicals and drugs of known toxicity. TPDB software enables i string searches for author names and proteins names/synonyms, ii more complex searches by selecting chemical compound, animal species, target tissue and protein names/synonyms from pull-down menus, and iii commonality searches over multiple chemicals. Tabulated search results provide information, references and links to other databases. Conclusion The TPDB is a unique on-line compilation of information on the covalent modification of cellular proteins by reactive metabolites of chemicals and drugs. Its comprehensiveness and searchability should facilitate the elucidation of mechanisms of reactive metabolite toxicity. The database is freely available at http://tpdb.medchem.ku.edu/tpdb.html

  3. Synthesis, characterisation and chemical reactivity of some new binuclear dioxouranium(VI) complexes derived from organic diazo compounds (Preprint No. CT-33)

    International Nuclear Information System (INIS)

    Pujar, M.A.; Pirgonde, B.R.

    1988-02-01

    A new series of binuclear dioxouranium(VI) complexes of polydentatate diazo compounds have been synthesised and characterised adequately by analysis, physio-chemical techniques and reactivity of these complexes. The location of bonding site of ligands, stability of complexes and status of U-O bond and probable structures of these complexes have been discussed. (author). 10 refs

  4. Modeling and simulation of reactive flows

    CERN Document Server

    Bortoli, De AL; Pereira, Felipe

    2015-01-01

    Modelling and Simulation of Reactive Flows presents information on modeling and how to numerically solve reactive flows. The book offers a distinctive approach that combines diffusion flames and geochemical flow problems, providing users with a comprehensive resource that bridges the gap for scientists, engineers, and the industry. Specifically, the book looks at the basic concepts related to reaction rates, chemical kinetics, and the development of reduced kinetic mechanisms. It considers the most common methods used in practical situations, along with equations for reactive flows, and va

  5. Comparison of Electrocoagulation and Chemical Coagulation Processes in Removing Reactive red 196 from Aqueous Solution

    Directory of Open Access Journals (Sweden)

    Ali Assadi

    2016-06-01

    Full Text Available Background: Conventional chemical coagulation is considered as an old method to dye and COD removal in textile effluent. Electrocoagulation (EC process is a robust method to achieve maximum removal. Methods: This study was designed to compare the result of operational parameters including optimum pH and coagulant concentration for chemical coagulation with ferric chloride and alum also, voltage, electrolysis time, initial pH, and conductivity for EC with iron electrodes to remove reactive red 196 (RR 196. Results: The outcomes show that ferric chloride and alum at optimum concentration were capable of removing dye and COD by 79.63 % and 84.83% and 53% and 55%, respectively. In contrast, EC process removed the dye and COD by 99.98% and 90.4%, respectively. Conclusion: The highest treatment efficiency was obtained by increasing the voltage, electrolysis time, pH and conductivity. Increase initial dye concentration reduces removal efficiency. Ultimately, it could be concluded that EC technology is an efficient procedure for handling of colored industrial wastewaters.

  6. Chemical reactivities of some interstellar molecules

    Energy Technology Data Exchange (ETDEWEB)

    Chadha, M S

    1980-01-01

    Work in the area of chemical evolution during the last 25 years has revealed the formation of a large number of biologically important molecules produced from simple starting materials under relatively simple experimental conditions. Much of this work has resulted from studies under atmospheres simulating that of the primitive earth or other planets. During the last decade, progress has also been made in the identification of chemical constituents of interstellar medium. A number of these molecules are the same as those identified in laboratory experiments. Even though the conditions of the laboratory experiments are vastly different from those of the cool, low-density interstellar medium, some of the similarities in composition are too obvious to go unnoticed. The present paper highlights some of the similarities in the composition of prebiotic molecules and those discovered in the interstellar medium. Also the chemical reactions which some of the common molecules e.g., NH3, HCN, H2CO, HC(triple bond)-C-CN etc. can undergo are surveyed.

  7. Thermal-mechanical-chemical responses of polymer-bonded explosives using a mesoscopic reactive model under impact loading.

    Science.gov (United States)

    Wang, XinJie; Wu, YanQing; Huang, FengLei

    2017-01-05

    A mesoscopic framework is developed to quantify the thermal-mechanical-chemical responses of polymer-bonded explosive (PBX) samples under impact loading. A mesoscopic reactive model is developed for the cyclotetramethylenetetranitramine (HMX) crystal, which incorporates nonlinear elasticity, crystal plasticity, and temperature-dependent chemical reaction. The proposed model was implemented in the finite element code ABAQUS by the user subroutine VUMAT. A series of three-dimensional mesoscale models were constructed and calculated under low-strength impact loading scenarios from 100m/s to 600m/s where only the first wave transit is studied. Crystal anisotropy and microstructural heterogeneity are responsible for the nonuniform stress field and fluctuations of the stress wave front. At a critical impact velocity (≥300m/s), a chemical reaction is triggered because the temperature contributed by the volumetric and plastic works is sufficiently high. Physical quantities, including stress, temperature, and extent of reaction, are homogenized from those across the microstructure at the mesoscale to compare with macroscale measurements, which will advance the continuum-level models. The framework presented in this study has important implications in understanding hot spot ignition processes and improving predictive capabilities in energetic materials. Copyright © 2016 Elsevier B.V. All rights reserved.

  8. Reactive transport models and simulation with ALLIANCES

    International Nuclear Information System (INIS)

    Leterrier, N.; Deville, E.; Bary, B.; Trotignon, L.; Hedde, T.; Cochepin, B.; Stora, E.

    2009-01-01

    Many chemical processes influence the evolution of nuclear waste storage. As a result, simulations based only upon transport and hydraulic processes fail to describe adequately some industrial scenarios. We need to take into account complex chemical models (mass action laws, kinetics...) which are highly non-linear. In order to simulate the coupling of these chemical reactions with transport, we use a classical Sequential Iterative Approach (SIA), with a fixed point algorithm, within the mainframe of the ALLIANCES platform. This approach allows us to use the various transport and chemical modules available in ALLIANCES, via an operator-splitting method based upon the structure of the chemical system. We present five different applications of reactive transport simulations in the context of nuclear waste storage: 1. A 2D simulation of the lixiviation by rain water of an underground polluted zone high in uranium oxide; 2. The degradation of the steel envelope of a package in contact with clay. Corrosion of the steel creates corrosion products and the altered package becomes a porous medium. We follow the degradation front through kinetic reactions and the coupling with transport; 3. The degradation of a cement-based material by the injection of an aqueous solution of zinc and sulphate ions. In addition to the reactive transport coupling, we take into account in this case the hydraulic retroaction of the porosity variation on the Darcy velocity; 4. The decalcification of a concrete beam in an underground storage structure. In this case, in addition to the reactive transport simulation, we take into account the interaction between chemical degradation and the mechanical forces (cracks...), and the retroactive influence on the structure changes on transport; 5. The degradation of the steel envelope of a package in contact with a clay material under a temperature gradient. In this case the reactive transport simulation is entirely directed by the temperature changes and

  9. Attenuation of Chemical Reactivity of Shale Matrixes following Scale Precipitation

    Science.gov (United States)

    Li, Q.; Jew, A. D.; Kohli, A. H.; Alalli, G.; Kiss, A. M.; Kovscek, A. R.; Zoback, M. D.; Brown, G. E.; Maher, K.; Bargar, J.

    2017-12-01

    Introduction of fracture fluids into shales initiates a myriad of fluid-rock reactions that can strongly influence migration of fluid and hydrocarbon through shale/fracture interfaces. Due to the extremely low permeability of shale matrixes, studies on chemical reactivity of shales have mostly focused on shale surfaces. Shale-fluid interactions inside within shale matrixes have not been examined, yet the matrix is the primary conduit through which hydrocarbons and potential contaminants are transmitted. To characterize changes in matrix mineralogy, porosity, diffusivity, and permeability during hydraulic stimulation, we reacted Marcellus (high clay and low carbonate) and Eagle Ford (low clay and high carbonate) shale cores with fracture fluids for 3 weeks at elevated pressure and temperature (80 oC, and 77 bars). In the carbonate-poor Marcellus system, fluid pH increased from 2 to 4, and secondary Fe(OH)3 precipitates were observed in the fluid. Sulfur X-ray fluorescence maps show that fluids had saturated and reacted with the entire 1-cm-diameter core. In the carbonate-rich Eagle Ford system, pH increased from 2 to 6 due to calcite dissolution. When additional Ba2+ and SO42- were present (log10(Q/K)=1.3), extensive barite precipitation was observed in the matrix of the Eagle Ford core (and on the surface). Barite precipitation was also observed on the surface of the Marcellus core, although to a lesser extent. In the Marcellus system, the presence of barite scale attenuated diffusivity in the matrix, as demonstrated by sharply reduced Fe leaching and much less sulfide oxidation. Systematic studies in homogeneous solution show that barite scale precipitation rates are highly sensitive to pH, salinity, and the presence of organic compounds. These findings imply that chemical reactions are not confined to shale/fluid interfaces but can penetrate into shale matrices, and that barite scale formation can clog diffusion pathways for both fluid and hydrocarbon.

  10. 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 ...

  11. Investigation on reactivity of iron nickel oxides in chemical looping dry reforming

    International Nuclear Information System (INIS)

    Huang, Zhen; He, Fang; Chen, Dezhen; Zhao, Kun; Wei, Guoqiang; Zheng, Anqing; Zhao, Zengli; Li, Haibin

    2016-01-01

    Iron nickel oxides as oxygen carriers were investigated to clarify the reaction mechanism of NiFe_2O_4 material during the chemical looping dry reforming (CLDR) process. The thermodynamic analysis showed that metallic Fe can be oxidized into Fe_3O_4 by CO_2, but metallic Ni cannot. The oxidizability of the four oxygen carriers was in the order of NiO > synthetic NiFe_2O_4 spinel > NiO-Fe_2O_3 mixed oxides > Fe_2O_3, and the reducibility sequence of their reduced products was synthetic NiFe_2O_4 spinel > NiO-Fe_2O_3 mixed oxides > Fe_2O_3 > NiO. The NiO showed the best oxidizability but it was easy to cause CH_4 cracking and its reduced product (Ni) did not recover lattice oxygen under CO_2 atmosphere. It only produced 74 mL CO for 1 g Fe_2O_3 during the CO_2 reforming because of its weak oxidizability. The Redox ability of synthetic NiFe_2O_4 was obvious higher than that of NiO-Fe_2O_3 mixed oxides due to the synergistic effect of metallic Fe-Ni in the spinel structure. 1 g synthetic NiFe_2O_4 can produce 238 mL CO, which was twice higher than that of 1 g NiO-Fe_2O_3 mixed oxides (111 mL). A part of Fe element was divorced from the NiFe_2O_4 spinel structure after one cycle, which was the major reason for degradation of reactivity of NiFe_2O_4 oxygen carrier. - Highlights: • A synergistic effect of Fe/Ni can improve the reactivity of oxygen carrier (OC). • The oxidizability sequence of four OCs is NiO > NiFe_2O_4 > mixed NiO + Fe_2O_3 > Fe_2O_3. • The reducibility sequence of four OCs is NiFe_2O_4 > mixed NiO + Fe_2O_3 > Fe_2O_3 > NiO. • The formation of Fe (Ni) alloy phase facilitates more CO_2 reduced into CO. • Part of Fe is divorced from the spinel structure, leading to the degeneration of OC reactivity.

  12. Abiotic pyrite reactivity versus nitrate, selenate and selenite using chemical and electrochemical methods

    International Nuclear Information System (INIS)

    Ignatiadis, I.; Betelu, S.; Gaucher, E.; Tournassat, C.; Chainet, F.

    2010-01-01

    Document available in extended abstract form only. This work is part of ReCosy European project (www.recosy.eu), whose main objectives are the sound understanding of redox phenomena controlling the long-term release/retention of radionuclides in nuclear waste disposal and providing tools to apply the results to performance assessment/safety case. Redox is one of the main factor affecting speciation and mobility of redox-sensitive radionuclides. Thus, it is of a great importance to investigate the redox reactivity of the host radioactive waste formations, particularly when exposed to redox perturbations. Callovo-Oxfordian formation (COx), a clay rock known as an anoxic and reducing system, was selected in France as the most suitable location to store nuclear waste. Iron (II) sulfide, mostly constituted of pyrite (FeS 2 ), iron (II) carbonate, iron(II) bearing clays and organic matter are considered to account almost entirely for the total reducing capacity of the rock. We report here the redox reactivity of pyrite upon exposure to nitrate (N(V)), selenate (Se(VI)) and selenite (Se(IV)) that possibly occur in the nuclear storage. Both, chemical and electrochemical kinetic approaches were simultaneously conducted such as to (i) determine the kinetics parameters of the reactions and (ii) understand the kinetic mechanisms. In order to reach similar conditions that are encountered in the storage system, all experiments were realised in NaCl 0.1 M, near neutral pH solutions, and an abiotic glove box (O 2 less than 10 -8 M). Chemical approach has consisted to set in contact pyrite in grains with solutions containing respectively nitrate, selenate and selenite. Reactants and products chemical analyses, conducted at different contact times, allowed us to assess the kinetics of oxidant reduction. Electrochemical approach has consisted in the continuous or semi-continuous analysis of large surface pyrite electrodes immersed in solutions with or without oxidant (nitrate

  13. Optimization of integrated chemical-biological degradation of a reactive azo dye using response surface methodology

    International Nuclear Information System (INIS)

    Sudarjanto, Gatut; Keller-Lehmann, Beatrice; Keller, Jurg

    2006-01-01

    The integrated chemical-biological degradation combining advanced oxidation by UV/H 2 O 2 followed by aerobic biodegradation was used to degrade C.I. Reactive Azo Red 195A, commonly used in the textile industry in Australia. An experimental design based on the response surface method was applied to evaluate the interactive effects of influencing factors (UV irradiation time, initial hydrogen peroxide dosage and recirculation ratio of the system) on decolourisation efficiency and optimizing the operating conditions of the treatment process. The effects were determined by the measurement of dye concentration and soluble chemical oxygen demand (S-COD). The results showed that the dye and S-COD removal were affected by all factors individually and interactively. Maximal colour degradation performance was predicted, and experimentally validated, with no recirculation, 30 min UV irradiation and 500 mg H 2 O 2 /L. The model predictions for colour removal, based on a three-factor/five-level Box-Wilson central composite design and the response surface method analysis, were found to be very close to additional experimental results obtained under near optimal conditions. This demonstrates the benefits of this approach in achieving good predictions while minimising the number of experiments required

  14. The iodine reactivity

    International Nuclear Information System (INIS)

    2003-01-01

    The iodine is an important element because it has long life isotopes (such as iodine 129) and a great mobility in natural media. Iodine presents a complex chemistry because of its volatility and its strong redox reactivity. The S.E.C.R. works to better understand the reactivity of this element in different natural, industrial or biological environments. It plays a part in thermochemical sites as a possible way of hydrogen formation. This seminar gives some aspects relative to the chemical reactivity of iodine, since its thermochemistry in the I/S cycles to produce hydrogen to its reactivity in the natural medium and its potential radiological impact. This document includes 4 presentations transparencies) dealing with: the 129 I cycle rejected in the low radioactive gaseous and liquid effluents of the La Hague reprocessing plant (C. Frechou); a bibliographic review of iodine retention in soils (F. Bazer-Bachi); the hydrogen production and the iodine/sulfur thermochemical cycle (role of iodine in the process); and the direct characterization by electro-spray ionization mass spectroscopy of iodine fixation by fulvic acids (P. Reiller, B. Amekraz, C. Moulin, V. Moulin)

  15. Establishment and intra-/inter-laboratory validation of a standard protocol of reactive oxygen species assay for chemical photosafety evaluation.

    Science.gov (United States)

    Onoue, Satomi; Hosoi, Kazuhiro; Wakuri, Shinobu; Iwase, Yumiko; Yamamoto, Toshinobu; Matsuoka, Naoko; Nakamura, Kazuichi; Toda, Tsuguto; Takagi, Hironori; Osaki, Naoto; Matsumoto, Yasuhiro; Kawakami, Satoru; Seto, Yoshiki; Kato, Masashi; Yamada, Shizuo; Ohno, Yasuo; Kojima, Hajime

    2013-11-01

    A reactive oxygen species (ROS) assay was previously developed for photosafety evaluation of pharmaceuticals, and the present multi-center study aimed to establish and validate a standard protocol for ROS assay. In three participating laboratories, two standards and 42 coded chemicals, including 23 phototoxins and 19 nonphototoxic drugs/chemicals, were assessed by the ROS assay according to the standardized protocol. Most phototoxins tended to generate singlet oxygen and/or superoxide under UV-vis exposure, but nonphototoxic chemicals were less photoreactive. In the ROS assay on quinine (200 µm), a typical phototoxic drug, the intra- and inter-day precisions (coefficient of variation; CV) were found to be 1.5-7.4% and 1.7-9.3%, respectively. The inter-laboratory CV for quinine averaged 15.4% for singlet oxygen and 17.0% for superoxide. The ROS assay on 42 coded chemicals (200 µm) provided no false negative predictions upon previously defined criteria as compared with the in vitro/in vivo phototoxicity, although several false positives appeared. Outcomes from the validation study were indicative of satisfactory transferability, intra- and inter-laboratory variability, and predictive capacity of the ROS assay. Copyright © 2012 John Wiley & Sons, Ltd.

  16. Spatially Resolved Quantification of the Surface Reactivity of Solid Catalysts.

    Science.gov (United States)

    Huang, Bing; Xiao, Li; Lu, Juntao; Zhuang, Lin

    2016-05-17

    A new property is reported that accurately quantifies and spatially describes the chemical reactivity of solid surfaces. The core idea is to create a reactivity weight function peaking at the Fermi level, thereby determining a weighted summation of the density of states of a solid surface. When such a weight function is defined as the derivative of the Fermi-Dirac distribution function at a certain non-zero temperature, the resulting property is the finite-temperature chemical softness, termed Fermi softness (SF ), which turns out to be an accurate descriptor of the surface reactivity. The spatial image of SF maps the reactive domain of a heterogeneous surface and even portrays morphological details of the reactive sites. SF analyses reveal that the reactive zones on a Pt3 Y(111) surface are the platinum sites rather than the seemingly active yttrium sites, and the reactivity of the S-dimer edge of MoS2 is spatially anisotropic. Our finding is of fundamental and technological significance to heterogeneous catalysis and industrial processes demanding rational design of solid catalysts. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Reactivity of a Pt(100) cluster modified by adsorption of a nickel tetramer

    Energy Technology Data Exchange (ETDEWEB)

    Ortiz, E V; Lopez, M B [Centro de Investigaciones Fisicoquimicas, Teoricas y Aplicadas (CIFTA), Facultad de Ciencias Exactas y Naturales, Universidad Nacional de Catamarca, Av. Belgrano 300, (4700), Catamarca (Argentina); Castro, E A, E-mail: mblopez@fcasuser.unca.edu.a [INIFTA, CONICET, Universidad Nacional de la Plata, Diag. 113 y 64, Suc.4, C.C. 16, (1900), La Plata (Argentina)

    2009-05-01

    The aim of this paper is to report a study of the reactivity of Pt(100) cluster and the same system modified by a nickel tetramer towards the atomic hydrogen adsorption. This study was carried out in the framework of density functional theory which provides global and local indexes that can be used to characterize the reactivity. The analyzed reactivity descriptors were: chemical potential, chemical hardness, electrophilicity index and Fukui function. The results showed that the global reactivity descriptor predicts that the platinum cluster modified by nickel is more reactive than the pure platinum cluster and that the local Fukui function provides information about the most susceptible site to electrophilic attack in platinum cluster.

  18. Borylnitrenes: electrophilic reactive intermediates with high reactivity towards C-H bonds.

    Science.gov (United States)

    Bettinger, Holger F; Filthaus, Matthias

    2010-12-21

    Borylnitrenes (catBN 3a and pinBN 3b; cat = catecholato, pin = pinacolato) are reactive intermediates that show high tendency towards insertion into the C-H bonds of unactivated hydrocarbons. The present article summarizes the matrix isolation investigations that were aimed at identifying, characterizing and investigating the chemical behaviour of 3a by spectroscopic means, and of the experiments in solution and in the gas phase that were performed with 3b. Comparison with the reactivity reported for difluorovinylidene 1a in solid argon indicates that 3a shows by and large similar reactivity, but only after photochemical excitation. The derivative 3b inserts into the C-H bonds of hydrocarbon solvents in high yields and thus allows the formation of primary amines, secondary amines, or amides from "unreactive" hydrocarbons. It can also be used for generation of methylamine or methylamide from methane in the gas phase at room temperature. Remaining challenges in the chemistry of borylnitrenes are briefly summarized.

  19. Revealing the importance of linkers in K-series oxime reactivators for tabun-inhibited AChE using quantum chemical, docking and SMD studies.

    Science.gov (United States)

    Ghosh, Shibaji; Chandar, Nellore Bhanu; Jana, Kalyanashis; Ganguly, Bishwajit

    2017-08-01

    Inhibition of acetylcholinesterase (AChE) with organophosphorus compounds has a detrimental effect on human life. Oxime K203 seems to be one of the promising reactivators for tabun-inhibited AChE than (K027, K127, and K628). These reactivators differ only in the linker units between the two pyridinium rings. The conformational analyses performed with quantum chemical RHF/6-31G* level for K027, K127, K203 and K628 showed that the minimum energy conformers have different orientations of the active and peripheral pyridinium rings for these reactivator molecules. K203 with (-CH 2 -CH=CH-CH 2 -) linker unit possesses more open conformation compared to the other reactivators. Such orientation of K203 experiences favorable interaction with the surrounding residues of catalytic anionic site (CAS) and peripheral anionic site (PAS) of tabun-inhibited AChE. From the steered molecular dynamics simulations, it has been observed that the oxygen atom of the oxime group of K203 reactivator approaches nearest to the P-atom of the SUN203 (3.75 Å) at lower time scales (less than ~1000 ps) as compared to the other reactivators. K203 experiences less number of hydrophobic interaction with the PAS residues which is suggested to be an important factor for the efficient reactivation process. In addition, K203 crates large number of H-bonding with CAS residues SUN203, Phe295, Tyr337, Phe338 and His447. K203 barely changes its conformation during the SMD simulation process and hence the energy penalty to adopt any other conformation is minimal in this case as compared to the other reactivators. The molecular mechanics and Poisson-Boltzmann surface area binding energies obtained for the interaction of K203 inside the gorge of tabun inhibited AChE is substantially higher (-290.2 kcal/mol) than the corresponding K628 reactivator (-260.4 kcal/mol), which also possess unsaturated aromatic linker unit.

  20. Revealing the importance of linkers in K-series oxime reactivators for tabun-inhibited AChE using quantum chemical, docking and SMD studies

    Science.gov (United States)

    Ghosh, Shibaji; Chandar, Nellore Bhanu; Jana, Kalyanashis; Ganguly, Bishwajit

    2017-08-01

    Inhibition of acetylcholinesterase (AChE) with organophosphorus compounds has a detrimental effect on human life. Oxime K203 seems to be one of the promising reactivators for tabun-inhibited AChE than (K027, K127, and K628). These reactivators differ only in the linker units between the two pyridinium rings. The conformational analyses performed with quantum chemical RHF/6-31G* level for K027, K127, K203 and K628 showed that the minimum energy conformers have different orientations of the active and peripheral pyridinium rings for these reactivator molecules. K203 with (-CH2-CH=CH-CH2-) linker unit possesses more open conformation compared to the other reactivators. Such orientation of K203 experiences favorable interaction with the surrounding residues of catalytic anionic site (CAS) and peripheral anionic site (PAS) of tabun-inhibited AChE. From the steered molecular dynamics simulations, it has been observed that the oxygen atom of the oxime group of K203 reactivator approaches nearest to the P-atom of the SUN203 (3.75 Å) at lower time scales (less than 1000 ps) as compared to the other reactivators. K203 experiences less number of hydrophobic interaction with the PAS residues which is suggested to be an important factor for the efficient reactivation process. In addition, K203 crates large number of H-bonding with CAS residues SUN203, Phe295, Tyr337, Phe338 and His447. K203 barely changes its conformation during the SMD simulation process and hence the energy penalty to adopt any other conformation is minimal in this case as compared to the other reactivators. The molecular mechanics and Poisson-Boltzmann surface area binding energies obtained for the interaction of K203 inside the gorge of tabun inhibited AChE is substantially higher (-290.2 kcal/mol) than the corresponding K628 reactivator (-260.4 kcal/mol), which also possess unsaturated aromatic linker unit.

  1. Major reactive species of ambient volatile organic compounds (VOCs) and their sources in Beijing

    Institute of Scientific and Technical Information of China (English)

    SHAO; Min; FU; Linlin; LIU; Ying; LU; Sihua; ZHANG; Yuanhan

    2005-01-01

    Volatile organic compounds (VOCs) are important precursors of atmospheric chemical processes. As a whole mixture, the ambient VOCs show very strong chemical reactivity. Based on OH radical loss rates in the air, the chemical reactivity of VOCs in Beijing was calculated. The results revealed that alkenes, accounting for only about 15% in the mixing ratio of VOCs, provide nearly 75% of the reactivity of ambient VOCs and the C4 to C5 alkenes were the major reactive species among the alkenes. The study of emission characteristics of various VOCs sources indicated that these alkenes are mainly from vehicle exhaust and gasoline evaporation. The reduction of alkene species in these two sources will be effective in photochemical pollution control in Beijing.

  2. Reactive Ion Etching as Cleaning Method Post Chemical Mechanical Polishing for Phase Change Memory Device

    International Nuclear Information System (INIS)

    Min, Zhong; Zhi-Tang, Song; Bo, Liu; Song-Lin, Feng; Bomy, Chen

    2008-01-01

    In order to improve nano-scale phase change memory performance, a super-clean interface should be obtained after chemical mechanical polishing (CMP) of Ge 2 Sb 2 Te 5 phase change films. We use reactive ion etching (RIE) as the cleaning method. The cleaning effect is analysed by scanning electron microscopy and an energy dispersive spectrometer. The results show that particle residue on the surface has been removed. Meanwhile, Ge 2 Sb 2 Te 5 material stoichiometric content ratios are unchanged. After the top electrode is deposited, current-voltage characteristics test demonstrates that the set threshold voltage is reduced from 13 V to 2.7V and the threshold current from 0.1mA to 0.025mA. Furthermore, we analyse the RIE cleaning principle and compare it with the ultrasonic method

  3. Reactive Chemical Vapor Deposition Method as New Approach for Obtaining Electroluminescent Thin Film Materials

    Directory of Open Access Journals (Sweden)

    Valentina V. Utochnikova

    2012-01-01

    Full Text Available The new reactive chemical vapor deposition (RCVD method has been proposed for thin film deposition of luminescent nonvolatile lanthanide aromatic carboxylates. This method is based on metathesis reaction between the vapors of volatile lanthanide dipivaloylmethanate (Ln(dpm3 and carboxylic acid (HCarb orH2Carb′ and was successfully used in case of HCarb. Advantages of the method were demonstrated on example of terbium benzoate (Tb(bz3 and o-phenoxybenzoate thin films, and Tb(bz3 thin films were successfully examined in the OLED with the following structure glass/ITO/PEDOT:PSS/TPD/Tb(bz3/Ca/Al. Electroluminescence spectra of Tb(bz3 showed only typical luminescent bands, originated from transitions of the terbium ion. Method peculiarities for deposition of compounds of dibasic acids H2Carb′ are established on example of terbium and europium terephtalates and europium 2,6-naphtalenedicarboxylate.

  4. Octazethrene and Its Isomer with Different Diradical Characters and Chemical Reactivity: The Role of the Bridge Structure

    KAUST Repository

    Hu, Pan

    2016-03-11

    The fundamental relationship between structure and diradical character is important for the development of open-shell diradicaloid-based materials. In this work, we synthesized two structural isomers bearing a 2,6-naphthoquinodimethane or a 1,5-naphthoquinodimethane bridge and demonstrated that their diradical characters and chemical reactivity are quite different. The mesityl or pentafluorophenyl substituted octazethrene derivatives OZ-M/OZ-F and their isomer OZI-M (with mesityl substituents) were synthesized via an intramolecular Friedel-Crafts alkylation followed by oxidative dehydrogenation strategy from the key building blocks 4 and 11. Our detailed experimental and theoretical studies showed that both isomers have an open-shell singlet ground state with a remarkable diradical character (y0 = 0.35 and 0.34 for OZ-M and OZ-F, and y0 = 0.58 for OZI-M). Compounds OZ-M and OZ-F have good stability under the ambient environment while OZI-M has high reactivity and can be easily oxidized to a dioxo-product 15, which can be correlated to their different diradical characters. Additionally, we investigated the physical properties of OZ-M, OZ-F and 15.

  5. A Model to Couple Flow, Thermal and Reactive Chemical Transport, and Geo-mechanics in Variably Saturated Media

    Science.gov (United States)

    Yeh, G. T.; Tsai, C. H.

    2015-12-01

    This paper presents the development of a THMC (thermal-hydrology-mechanics-chemistry) process model in variably saturated media. The governing equations for variably saturated flow and reactive chemical transport are obtained based on the mass conservation principle of species transport supplemented with Darcy's law, constraint of species concentration, equation of states, and constitutive law of K-S-P (Conductivity-Degree of Saturation-Capillary Pressure). The thermal transport equation is obtained based on the conservation of energy. The geo-mechanic displacement is obtained based on the assumption of equilibrium. Conventionally, these equations have been implicitly coupled via the calculations of secondary variables based on primary variables. The mechanisms of coupling have not been obvious. In this paper, governing equations are explicitly coupled for all primary variables. The coupling is accomplished via the storage coefficients, transporting velocities, and conduction-dispersion-diffusion coefficient tensor; one set each for every primary variable. With this new system of equations, the coupling mechanisms become clear. Physical interpretations of every term in the coupled equations will be discussed. Examples will be employed to demonstrate the intuition and superiority of these explicit coupling approaches. Keywords: Variably Saturated Flow, Thermal Transport, Geo-mechanics, Reactive Transport.

  6. Octazethrene and Its Isomer with Different Diradical Characters and Chemical Reactivity: The Role of the Bridge Structure

    KAUST Repository

    Hu, Pan; Lee, Sangsu; Park, Kyu Hyung; Das, Soumyajit; Herng, Tun Seng; Goncalves, Theo; Huang, Kuo-Wei; Ding, Jun; Kim, Dongho; Wu, Jishan

    2016-01-01

    The fundamental relationship between structure and diradical character is important for the development of open-shell diradicaloid-based materials. In this work, we synthesized two structural isomers bearing a 2,6-naphthoquinodimethane or a 1,5-naphthoquinodimethane bridge and demonstrated that their diradical characters and chemical reactivity are quite different. The mesityl or pentafluorophenyl substituted octazethrene derivatives OZ-M/OZ-F and their isomer OZI-M (with mesityl substituents) were synthesized via an intramolecular Friedel-Crafts alkylation followed by oxidative dehydrogenation strategy from the key building blocks 4 and 11. Our detailed experimental and theoretical studies showed that both isomers have an open-shell singlet ground state with a remarkable diradical character (y0 = 0.35 and 0.34 for OZ-M and OZ-F, and y0 = 0.58 for OZI-M). Compounds OZ-M and OZ-F have good stability under the ambient environment while OZI-M has high reactivity and can be easily oxidized to a dioxo-product 15, which can be correlated to their different diradical characters. Additionally, we investigated the physical properties of OZ-M, OZ-F and 15.

  7. Quick Look Report for Chemical Reactivity Modeling of Various Multi-Canister Overpack Breaches

    International Nuclear Information System (INIS)

    Bratton, Robert Lawrence

    2002-01-01

    This report makes observations or shows trends in the response and does not specifically provide conclusions or predict the onset of bulk uranium oxidation safety margins based on hole size. Comprehensive analysis will be provided in the future. The report should animate discussions about the results and what should be analyzed further in the final analysis. This report intends only to show the response of the breached multi-canister overpack (MCO) as a function of event time using the GOTH( ) SNF computer code. The response will be limited to physical quantities available on the exterior of the MCO. The GOTH( ) SNF model is approximate, because not all physical phenomenon was included in the model. Error estimates in the response are not possible at this time, because errors in the actual physical data are not known. Sensitivities in the results from variations in the physical data have not been pursued at this time, either. This effort was undertaken by the National Spent Nuclear Fuel Program to evaluate potential chemical reactivity issues of a degraded uranium metal spent nuclear fuel using the MCO fully loaded with Mark IV N-reactor fuel as the evaluation model. This configuration is proposed for handling in the Yucca Mountain Project (YMP) surface facility. Hanford is loading N-reactor fuel elements into the MCO for interim storage at the Hanford site with permanent disposal proposed at YMP. A portion of the N-reactor fuel inventory has suffered corrosion, exposing the uranium metal under the zircaloy cladding. Because of the sealed MCO, the local radiation field, and decay heat of the fuel, hydrogen production cannot be ruled out from the metal hydrates on the surface of the zircaloy cladding and exposed fuel. Because of the much greater surface area, the oxyhydroxide composition, and water of hydration in the uranium metal corrosion product, the corrosion product will be a significant water source that may equal the absorbed water on the zircaloy cladding

  8. Quick Look Report for Chemical Reactivity Modeling of Various Multi-Canister Overpack Breaches

    Energy Technology Data Exchange (ETDEWEB)

    Bratton, Robert Lawrence

    2002-04-01

    This report makes observations or shows trends in the response and does not specifically provide conclusions or predict the onset of bulk uranium oxidation safety margins based on hole size. Comprehensive analysis will be provided in the future. The report should animate discussions about the results and what should be analyzed further in the final analysis. This report intends only to show the response of the breached multi-canister overpack (MCO) as a function of event time using the GOTH_SNF computer code. The response will be limited to physical quantities available on the exterior of the MCO. The GOTH_SNF model is approximate, because not all physical phenomenon was included in the model. Error estimates in the response are not possible at this time, because errors in the actual physical data are not known. Sensitivities in the results from variations in the physical data have not been pursued at this time, either. This effort was undertaken by the National Spent Nuclear Fuel Program to evaluate potential chemical reactivity issues of a degraded uranium metal spent nuclear fuel using the MCO fully loaded with Mark IV N-reactor fuel as the evaluation model. This configuration is proposed for handling in the Yucca Mountain Project (YMP) surface facility. Hanford is loading N-reactor fuel elements into the MCO for interim storage at the Hanford site with permanent disposal proposed at YMP. A portion of the N-reactor fuel inventory has suffered corrosion, exposing the uranium metal under the zircaloy cladding. Because of the sealed MCO, the local radiation field, and decay heat of the fuel, hydrogen production cannot be ruled out from the metal hydrates on the surface of the zircaloy cladding and exposed fuel. Because of the much greater surface area, the oxyhydroxide composition, and water of hydration in the uranium metal corrosion product, the corrosion product will be a significant water source that may equal the absorbed water on the zircaloy cladding. A

  9. Measurements of total OH reactivity during PROPHET-AMOS 2016

    Science.gov (United States)

    Rickly, P.; Sakowski, J.; Bottorff, B.; Lew, M.; Stevens, P. S.; Sklaveniti, S.; Locoge, N.; Dusanter, S.

    2017-12-01

    As one of the main oxidant in the atmosphere, the hydroxyl radical (OH) initiates the oxidation of volatile organic compounds that can lead to the formation of ozone and secondary organic aerosols. Understanding both the sources and sinks of OH is therefore important to address issues related to air quality and climate change. Measurements of total OH reactivity can provide an important test of our understanding of the OH radical budget. Recent measurements of total reactivity in many environments have been greater than calculated based on the measured concentration of VOCs, suggesting that important OH sinks in these environments are not well characterized. Measurements of total OH reactivity were performed in a forested environment during the PROPHET - AMOS field campaign (Program for Research on Oxidants: PHotochemisty, Emissions, and Transport - Atmospheric Measurements of Oxidants in Summer) using the Comparative Reactivity Method (CRM) and the Total OH Loss Rate Method (TOHLM). The site is characterized by large emissions of isoprene and monoterpenes and low anthropogenic influence. Measurements of total OH reactivity using these two techniques agree to within their respective uncertainties, giving confidence in the measured OH reactivity. In addition, measurements of trace gases (VOCs, NOx, O3) were used to perform a comprehensive apportionment of OH sinks. These measurements are used in a chemical model using the Master Chemical Mechanism to calculate the expected OH reactivity. The results will be compared to previous measurements of total OH reactivity at this site.

  10. Continuous flow chemistry: a discovery tool for new chemical reactivity patterns.

    Science.gov (United States)

    Hartwig, Jan; Metternich, Jan B; Nikbin, Nikzad; Kirschning, Andreas; Ley, Steven V

    2014-06-14

    Continuous flow chemistry as a process intensification tool is well known. However, its ability to enable chemists to perform reactions which are not possible in batch is less well studied or understood. Here we present an example, where a new reactivity pattern and extended reaction scope has been achieved by transferring a reaction from batch mode to flow. This new reactivity can be explained by suppressing back mixing and precise control of temperature in a flow reactor set up.

  11. Continuous flow chemistry: a discovery tool for new chemical reactivity patterns

    OpenAIRE

    Hartwig, Jan; Metternich, Jan B.; Nikbin, Nikzad; Kirschning, Andreas; Ley, Steven V.

    2014-01-01

    Continuous flow chemistry as a process intensification tool is well known. However, its ability to enable chemists to perform reactions which are not possible in batch is less well studied or understood. Here we present an example, where a new reactivity pattern and extended reaction scope has been achieved by transferring a reaction from batch mode to flow. This new reactivity can be explained by suppressing back mixing and precise control of temperature in a flow reactor set up.

  12. Optimization of integrated chemical-biological degradation of a reactive azo dye using response surface methodology

    Energy Technology Data Exchange (ETDEWEB)

    Sudarjanto, Gatut [Advanced Wastewater Management Centre, The University of Queensland, Qld 4072 (Australia); Keller-Lehmann, Beatrice [Advanced Wastewater Management Centre, The University of Queensland, Qld 4072 (Australia); Keller, Jurg [Advanced Wastewater Management Centre, The University of Queensland, Qld 4072 (Australia)]. E-mail: j.keller@awmc.uq.edu.au

    2006-11-02

    The integrated chemical-biological degradation combining advanced oxidation by UV/H{sub 2}O{sub 2} followed by aerobic biodegradation was used to degrade C.I. Reactive Azo Red 195A, commonly used in the textile industry in Australia. An experimental design based on the response surface method was applied to evaluate the interactive effects of influencing factors (UV irradiation time, initial hydrogen peroxide dosage and recirculation ratio of the system) on decolourisation efficiency and optimizing the operating conditions of the treatment process. The effects were determined by the measurement of dye concentration and soluble chemical oxygen demand (S-COD). The results showed that the dye and S-COD removal were affected by all factors individually and interactively. Maximal colour degradation performance was predicted, and experimentally validated, with no recirculation, 30 min UV irradiation and 500 mg H{sub 2}O{sub 2}/L. The model predictions for colour removal, based on a three-factor/five-level Box-Wilson central composite design and the response surface method analysis, were found to be very close to additional experimental results obtained under near optimal conditions. This demonstrates the benefits of this approach in achieving good predictions while minimising the number of experiments required.

  13. Chemical reactivity of cation-exchanged zeolites

    NARCIS (Netherlands)

    Pidko, E.A.

    2008-01-01

    Zeolites modified with metal cations have been extensively studied during the last two decades because of their wide application in different technologically important fields such as catalysis, adsorption and gas separation. Contrary to the well-understood mechanisms of chemical reactions catalyzed

  14. Molecular Electron Density Theory: A Modern View of Reactivity in Organic Chemistry.

    Science.gov (United States)

    Domingo, Luis R

    2016-09-30

    A new theory for the study of the reactivity in Organic Chemistry, named Molecular Electron Density Theory (MEDT), is proposed herein. MEDT is based on the idea that while the electron density distribution at the ground state is responsible for physical and chemical molecular properties, as proposed by the Density Functional Theory (DFT), the capability for changes in electron density is responsible for molecular reactivity. Within MEDT, the reactivity in Organic Chemistry is studied through a rigorous quantum chemical analysis of the changes of the electron density as well as the energies associated with these changes along the reaction path in order to understand experimental outcomes. Studies performed using MEDT allow establishing a modern rationalisation and to gain insight into molecular mechanisms and reactivity in Organic Chemistry.

  15. Hazards in the chemical laboratory

    International Nuclear Information System (INIS)

    Bretherick, L.

    1987-01-01

    The contents of this book are: Preface; Introduction; Health and Safety at Work Act 1974; Safety Planning and Management; Fire Protection; Reactive Chemical Hazards; Chemical Hazards and Toxicology; Health Care and First Aid; Hazardous Chemicals; Precautions against Radiations; and An American View

  16. Role of Chemical Reactivity and Transition State Modeling for Virtual Screening.

    Science.gov (United States)

    Karthikeyan, Muthukumarasamy; Vyas, Renu; Tambe, Sanjeev S; Radhamohan, Deepthi; Kulkarni, Bhaskar D

    2015-01-01

    Every drug discovery research program involves synthesis of a novel and potential drug molecule utilizing atom efficient, economical and environment friendly synthetic strategies. The current work focuses on the role of the reactivity based fingerprints of compounds as filters for virtual screening using a tool ChemScore. A reactant-like (RLS) and a product- like (PLS) score can be predicted for a given compound using the binary fingerprints derived from the numerous known organic reactions which capture the molecule-molecule interactions in the form of addition, substitution, rearrangement, elimination and isomerization reactions. The reaction fingerprints were applied to large databases in biology and chemistry, namely ChEMBL, KEGG, HMDB, DSSTox, and the Drug Bank database. A large network of 1113 synthetic reactions was constructed to visualize and ascertain the reactant product mappings in the chemical reaction space. The cumulative reaction fingerprints were computed for 4000 molecules belonging to 29 therapeutic classes of compounds, and these were found capable of discriminating between the cognition disorder related and anti-allergy compounds with reasonable accuracy of 75% and AUC 0.8. In this study, the transition state based fingerprints were also developed and used effectively for virtual screening in drug related databases. The methodology presented here provides an efficient handle for the rapid scoring of molecular libraries for virtual screening.

  17. Wiley guide to chemical incompatibilities

    National Research Council Canada - National Science Library

    Pohanish, Richard P; Greene, Stanley A

    2009-01-01

    .... A portable and easy-to-use reference on reactive substances commonly found in commerce, the Wiley Guide to Chemical Incompatibilities, Third Edition compiles hard-to-find data on over 11,000 chemical...

  18. 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.

  19. Permeable reactive barriers for pollutant removal from groundwater

    International Nuclear Information System (INIS)

    Simon, F.G.; Meggyes, T.

    2001-01-01

    The removal of pollutants from the groundwater using permeable reactive barriers is a novel in-situ groundwater remediation technology. The most relevant decontamination processes used are chemical reduction, oxidation, precipitation and sorption, for which examples are given. Some common organic pollutants are halogenated hydrocarbons, aromatic and nitroaromatic compounds which can be treated in reactive barriers successfully. Lead, chromium and, in particular, uranium are dealt with in great detail among inorganic pollutants because of their occurrence in many European countries. Construction methods for cut-off walls and reactive barriers exhibit similar features. Apart from conventional methods, drilling, deep soil mixing, jet technology, arrays of wells, injected systems and biobarriers are applied to construct permeable reactive barriers. Permeable reactive barriers bear great potential for the future in remediation engineering. (orig.)

  20. Practical use of chemical probes for reactive oxygen species produced in biological systems by {gamma}-irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Min Hee; Moon, Yu Ran; Chung, Byung Yeoup; Kim, Jae-Sung [Radiation Research Division for Bio-technology, Korea Atomic Energy Research Institute, 1266 Sinjeong-dong, Jeongeup-si, Jeollabuk-do 580-185 (Korea, Republic of); Lee, Kang-Soo [Crop Production and Technology Major, Chonbuk National University, Jeonju 561-756 (Korea, Republic of); Cho, Jae-Young [Bio-environmental Science Major, Chonbuk National University, Jeonju 561-756 (Korea, Republic of); Kim, Jin-Hong [Radiation Research Division for Bio-technology, Korea Atomic Energy Research Institute, 1266 Sinjeong-dong, Jeongeup-si, Jeollabuk-do 580-185 (Korea, Republic of)], E-mail: jhongkim@kaeri.re.kr

    2009-05-15

    Application of chemical probes, for detection of reactive oxygen species (ROS), was tested during {gamma}-irradiation. The ethanol/{alpha}-(4-pyridyl-1-oxide)-N-tert-butylnitrone (4-POBN) and 3,3'-diaminobenzidine (DAB) were structurally stable enough to detect {sup {center_dot}}OH and H{sub 2}O{sub 2}, increasingly generated by {gamma}-irradiation up to 1000 Gy. Interestingly, the production rate of H{sub 2}O{sub 2}, but not {sup {center_dot}}OH, during {gamma}-irradiation, was significantly different between in vitro systems of lettuce and spinach. These results suggest that 4-POBN and DAB could be utilized as a semi-quantitative probe to quantify {sup {center_dot}}OH and H{sub 2}O{sub 2}, produced by {gamma}-irradiation up to 1000 Gy.

  1. Analyzing relationships between surface perturbations and local chemical reactivity of metal sites: Alkali promotion of O2 dissociation on Ag(111)

    Science.gov (United States)

    Xin, Hongliang; Linic, Suljo

    2016-06-01

    Many commercial heterogeneous catalysts are complex structures that contain metal active sites promoted by multiple additives. Developing fundamental understanding about the impact of these perturbations on the local surface reactivity is crucial for catalyst development and optimization. In this contribution, we develop a general framework for identifying underlying mechanisms that control the changes in the surface reactivity of a metal site (more specifically the adsorbate-surface interactions) upon a perturbation in the local environment. This framework allows us to interpret fairly complex interactions on metal surfaces in terms of specific, physically transparent contributions that can be evaluated independently of each other. We use Cs-promoted dissociation of O2 as an example to illustrate our approach. We concluded that the Cs adsorbate affects the outcome of the chemical reaction through a strong alkali-induced electric field interacting with the static dipole moment of the O2/Ag(111) system.

  2. Molecular Electron Density Theory: A Modern View of Reactivity in Organic Chemistry

    Directory of Open Access Journals (Sweden)

    Luis R. Domingo

    2016-09-01

    Full Text Available A new theory for the study of the reactivity in Organic Chemistry, named Molecular Electron Density Theory (MEDT, is proposed herein. MEDT is based on the idea that while the electron density distribution at the ground state is responsible for physical and chemical molecular properties, as proposed by the Density Functional Theory (DFT, the capability for changes in electron density is responsible for molecular reactivity. Within MEDT, the reactivity in Organic Chemistry is studied through a rigorous quantum chemical analysis of the changes of the electron density as well as the energies associated with these changes along the reaction path in order to understand experimental outcomes. Studies performed using MEDT allow establishing a modern rationalisation and to gain insight into molecular mechanisms and reactivity in Organic Chemistry.

  3. Comparative Studies on Dyeability with Direct, Acid and Reactive Dyes after Chemical Modification of Jute with Mixed Amino Acids Obtained from Extract of Waste Soya Bean Seeds

    Science.gov (United States)

    Bhaumik, Nilendu Sekhar; Konar, Adwaita; Roy, Alok Nath; Samanta, Ashis Kumar

    2017-12-01

    Jute fabric was treated with mixed natural amino acids obtained from waste soya bean seed extract for chemical modification of jute for its cataionization and to enhance its dyeability with anionic dyes (like direct, reactive and acid dye) as well enabling soya modified jute for salt free dyeing with anionic reactive dyes maintaining its eco-friendliness. Colour interaction parameters including surface colour strength were assessed and compared for both bleached and soya-modified jute fabric for reactive dyeing and compared with direct and acid dye. Improvement in K/S value (surface colour strength) was observed for soya-modified jute even in absence of salt applied in dye bath for reactive dyes as well as for direct and acid dyes. In addition, reactive dye also shows good dyeability even in acid bath in salt free conditions. Colour fastness to wash was evaluated for bleached and soya-modified jute fabric after dyeing with direct, acid and reactive dyes are reported. Treatment of jute with soya-extracted mixed natural amino acids showed anchoring of some amino/aldemine groups on jute cellulosic polymer evidenced from Fourier Transform Infra-Red (FTIR) Spectroscopy. This amino or aldemine group incorporation in bleached jute causes its cationization and hence when dyed in acid bath for reactive dye (instead of conventional alkali bath) showed dye uptake for reactive dyes. Study of surface morphology by Scanning Electron Microscopy (SEM) of said soya-modified jute as compared to bleached jute was studied and reported.

  4. Dynamics of Reactive Microbial Hotspots in Concentration Gradient.

    Science.gov (United States)

    Hubert, A.; Farasin, J.; Tabuteau, H.; Dufresne, A.; Meheust, Y.; Le Borgne, T.

    2017-12-01

    In subsurface environments, bacteria play a major role in controlling the kinetics of a broad range of biogeochemical reactions. In such environments, nutrients fluxes and solute concentrations needed for bacteria metabolism may be highly variable in space and intermittent in time. This can lead to the formation of reactive hotspots where and when conditions are favorable to particular microorganisms, hence inducing biogeochemical reaction kinetics that differ significantly from those measured in homogeneous model environments. To investigate the impact of chemical gradients on the spatial structure and temporal dynamics of subsurface microorganism populations, we develop microfluidic cells allowing for a precise control of flow and chemical gradient conditions, as well as quantitative monitoring of the bacteria's spatial distribution and biofilm development. Using the non-motile Escherichia coli JW1908-1 strain and Gallionella capsiferriformans ES-2 as model organisms, we investigate the behavior and development of bacteria over a range of single and double concentration gradients in the concentrations of nutrients, electron donors and electron acceptors. We measure bacterial activity and population growth locally in precisely known hydrodynamic and chemical environments. This approach allows time-resolved monitoring of the location and intensity of reactive hotspots in micromodels as a function of the flow and chemical gradient conditions. We compare reactive microbial hotspot dynamics in our micromodels to classic growth laws and well-known growth parameters for the laboratory model bacteria Escherichia coli.We also discuss consequences for the formation and temporal dynamics of biofilms in the subsurface.

  5. Comparison of Chemical and Physical-chemical Wastewater Discoloring Methods

    Directory of Open Access Journals (Sweden)

    Durašević, V.

    2007-11-01

    Full Text Available Today's chemical and physical-chemical wastewater discoloration methods do not completely meet demands regarding degree of discoloration. In this paper discoloration was performed using Fenton (FeSO4 . 7 H2O + H2O2 + H2SO4 and Fenton-like (FeCl3 . 6 H2O + H2O2 + HCOOH chemical methods and physical-chemical method of coagulation/flocculation (using poly-electrolyte (POEL combining anion active coagulant (modified poly-acrylamides and cationic flocculant (product of nitrogen compounds in combination with adsorption on activated carbon. Suitability of aforementioned methods was investigated on reactive and acid dyes, regarding their most common use in the textile industry. Also, investigations on dyes of different chromogen (anthraquinone, phthalocyanine, azo and xanthene were carried out in order to determine the importance of molecular spatial structure. Oxidative effect of Fenton and Fenton-like reagents resulted in decomposition of colored chromogen and high degree of discoloration. However, the problem is the inability of adding POEL in stechiometrical ratio (also present in physical-chemical methods, when the phenomenon of overdosing coagulants occurs in order to obtain a higher degree of discoloration, creating a potential danger of burdening water with POEL. Input and output water quality was controlled through spectrophotometric measurements and standard biological parameters. In addition, part of the investigations concerned industrial wastewaters obtained from dyeing cotton materials using reactive dye (C. I. Reactive Blue 19, a process that demands the use of vast amounts of electrolytes. Also, investigations of industrial wastewaters was labeled as a crucial step carried out in order to avoid serious misassumptions and false conclusions, which may arise if dyeing processes are only simulated in the laboratory.

  6. Thermogravimetric study on the influence of structural, textural and chemical properties of biomass chars on CO2 gasification reactivity

    International Nuclear Information System (INIS)

    Bouraoui, Zeineb; Jeguirim, Mejdi; Guizani, Chamseddine; Limousy, Lionel; Dupont, Capucine; Gadiou, Roger

    2015-01-01

    The present investigation aims to examine the influence of textural, structural and chemical properties of biomass chars on the CO 2 gasification rate. Various lignocellulosic biomass chars were prepared under the same conditions. Different analytical techniques were used to determine the char properties such as Scanning Electronic Microscopy, nitrogen adsorption manometry, Raman spectroscopy and X Ray Fluorescence. Gasification tests were carried out in a thermobalance under 20% CO 2 in nitrogen at 800 °C. Significant differences of the total average reactivity were observed with a factor of 2 between the prepared chars. Moreover, different behaviors of gasification rate profiles versus conversion were obtained. This difference of behavior appeared to be correlated with the biomass char properties. Hence, up to 70% of conversion, the gasification rate was shown to depend on the char external surface and the potassium content. At higher conversion ratio, a satisfactory correlation between the Catalytic Index and the average gasification rate was identified. The results highlight the importance of knowing both textural and structural properties and mineral contents of biomass chars to predict fuel reactivity during CO 2 gasification processes. Such behavior prediction is highly important in the gasifiers design for char conversion. - Highlights: • CO 2 gasification reactivity of various lignocellulosic chars were examined. • Chars properties affect strongly samples gasification behavior. • Initial gasification rate is affected by external surface, K content and D3/G ratio. • Gasification rate behavior depends on the Alkali index at high conversion

  7. Effect of reactive and un-reactive substrates on photopolymerization of self-etching adhesives with different aggressiveness.

    Science.gov (United States)

    Zhang, Ying; Wang, Yong

    2013-01-01

    The study investigated the influence of reactive (enamel) and un-reactive (glass) substrates on photo-polymerization of self-etching adhesives. Two commercial adhesives Adper Prompt L-Pop (APLP, pH~0.8) and Adper Easy Bond (AEB, pH~2.5) were applied onto prepared enamel and glass substrates using the same protocol. Micro-Raman spectroscopy was employed to determine the degree of conversion (DC) and the involved mechanism. DC of APLP was dramatically enhanced from ~9.4% to ~82.0% as when changing from glass to enamel, while DC of AEB on both substrates showed no difference. The DC distributions along the adhesive layers of the APLP and AEB on enamel showed descending and constant trends, respectively. Spectral analysis disclosed that the difference in chemical reaction of the two adhesives with enamel might be associated with the results. The chemical reaction of the adhesives with enamel significantly improved the DC of the strong APLP, but not that of the mild AEB.

  8. Framework for reactive mass transport

    DEFF Research Database (Denmark)

    Jensen, Mads Mønster; Johannesson, Björn; Geiker, Mette Rica

    2014-01-01

    Reactive transport modeling is applicable for a range of porous materials. Here the modeling framework is focused on cement-based materials, where ion diffusion and migration are described by the Poisson-Nernst-Planck equation system. A two phase vapor/liquid flow model, with a sorption hysteresis...... description is coupled to the system. The mass transport is solved by using the finite element method where the chemical equilibrium is solved explicitly by an operator splitting method. The IPHREEQC library is used as chemical equilibrium solver. The equation system, solved by IPHREEQC, is explained...

  9. Complex Chemical Reaction Networks from Heuristics-Aided Quantum Chemistry.

    Science.gov (United States)

    Rappoport, Dmitrij; Galvin, Cooper J; Zubarev, Dmitry Yu; Aspuru-Guzik, Alán

    2014-03-11

    While structures and reactivities of many small molecules can be computed efficiently and accurately using quantum chemical methods, heuristic approaches remain essential for modeling complex structures and large-scale chemical systems. Here, we present a heuristics-aided quantum chemical methodology applicable to complex chemical reaction networks such as those arising in cell metabolism and prebiotic chemistry. Chemical heuristics offer an expedient way of traversing high-dimensional reactive potential energy surfaces and are combined here with quantum chemical structure optimizations, which yield the structures and energies of the reaction intermediates and products. Application of heuristics-aided quantum chemical methodology to the formose reaction reproduces the experimentally observed reaction products, major reaction pathways, and autocatalytic cycles.

  10. Reactive Distillation for Esterification of Bio-based Organic Acids

    Energy Technology Data Exchange (ETDEWEB)

    Fields, Nathan; Miller, Dennis J.; Asthana, Navinchandra S.; Kolah, Aspi K.; Vu, Dung; Lira, Carl T.

    2008-09-23

    The following is the final report of the three year research program to convert organic acids to their ethyl esters using reactive distillation. This report details the complete technical activities of research completed at Michigan State University for the period of October 1, 2003 to September 30, 2006, covering both reactive distillation research and development and the underlying thermodynamic and kinetic data required for successful and rigorous design of reactive distillation esterification processes. Specifically, this project has led to the development of economical, technically viable processes for ethyl lactate, triethyl citrate and diethyl succinate production, and on a larger scale has added to the overall body of knowledge on applying fermentation based organic acids as platform chemicals in the emerging biorefinery. Organic acid esters constitute an attractive class of biorenewable chemicals that are made from corn or other renewable biomass carbohydrate feedstocks and replace analogous petroleum-based compounds, thus lessening U.S. dependence on foreign petroleum and enhancing overall biorefinery viability through production of value-added chemicals in parallel with biofuels production. Further, many of these ester products are candidates for fuel (particularly biodiesel) components, and thus will serve dual roles as both industrial chemicals and fuel enhancers in the emerging bioeconomy. The technical report from MSU is organized around the ethyl esters of four important biorenewables-based acids: lactic acid, citric acid, succinic acid, and propionic acid. Literature background on esterification and reactive distillation has been provided in Section One. Work on lactic acid is covered in Sections Two through Five, citric acid esterification in Sections Six and Seven, succinic acid in Section Eight, and propionic acid in Section Nine. Section Ten covers modeling of ester and organic acid vapor pressure properties using the SPEAD (Step Potential

  11. Quantitative structure–reactivity study on sulfonation of amines, alcohols and phenols

    Directory of Open Access Journals (Sweden)

    Abolghasem Beheshti

    2017-05-01

    Full Text Available Quantitative structure–reactivity relationship (QSRR can be considered as a variant of quantitative structure property relationship (QSPR studies, where the chemical reactivity of reactants in a specified chemical reaction is related to chemical structure. As follows, the sulfonation reaction yield of 24 amines, alcohols and phenols with sulfonyl chloride was studied by QSRR. Quantum chemical calculations (b3lyp/6-31+g (d were carried out to obtain the optimized geometry. The suitable set of molecular descriptors was calculated to represent the molecular structures of compounds, such as constitutional, topological, geometrical, electrostatic and quantum-chemical descriptors. The genetic algorithm (GA was applied to select the variables that resulted in the best-fitted models. After the variable selection, multiple linear regression (MLR was utilized to construct linear QSRR models. The maximum relative error in prediction (5.26 showed that the predictive ability of the model was satisfactory and it can be used for designing similar reactants with efficient sulfonation reaction.

  12. Applications of the Conceptual Density Functional Theory Indices to Organic Chemistry Reactivity.

    Science.gov (United States)

    Domingo, Luis R; Ríos-Gutiérrez, Mar; Pérez, Patricia

    2016-06-09

    Theoretical reactivity indices based on the conceptual Density Functional Theory (DFT) have become a powerful tool for the semiquantitative study of organic reactivity. A large number of reactivity indices have been proposed in the literature. Herein, global quantities like the electronic chemical potential μ, the electrophilicity ω and the nucleophilicity N indices, and local condensed indices like the electrophilic P k + and nucleophilic P k - Parr functions, as the most relevant indices for the study of organic reactivity, are discussed.

  13. Chemistry of the 8-Nitroguanine DNA Lesion: Reactivity, Labelling and Repair.

    Science.gov (United States)

    Alexander, Katie J; McConville, Matthew; Williams, Kathryn R; Luzyanin, Konstantin V; O'Neil, Ian A; Cosstick, Richard

    2018-02-26

    The 8-nitroguanine lesion in DNA is increasingly associated with inflammation-related carcinogenesis, whereas the same modification on guanosine 3',5'-cyclic monophosphate generates a second messenger in NO-mediated signal transduction. Very little is known about the chemistry of 8-nitroguanine nucleotides, despite the fact that their biological effects are closely linked to their chemical properties. To this end, a selection of chemical reactions have been performed on 8-nitroguanine nucleosides and oligodeoxynucleotides. Reactions with alkylating reagents reveal how the 8-nitro substituent affects the reactivity of the purine ring, by significantly decreasing the reactivity of the N2 position, whilst the relative reactivity at N1 appears to be enhanced. Interestingly, the displacement of the nitro group with thiols results in an efficient and specific method of labelling this lesion and is demonstrated in oligodeoxynucleotides. Additionally, the repair of this lesion is also shown to be a chemically feasible reaction through a reductive denitration with a hydride source. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Process Improvement of Reactive Dye Synthesis Using Six Sigma Concept

    Science.gov (United States)

    Suwanich, Thanapat; Chutima, Parames

    2017-06-01

    This research focuses on the problem occurred in the reactive dye synthesis process of a global manufacturer in Thailand which producing various chemicals for reactive dye products to supply global industries such as chemicals, textiles and garments. The product named “Reactive Blue Base” is selected in this study because it has highest demand and the current chemical yield shows a high variation, i.e. yield variation of 90.4% - 99.1% (S.D. = 2.405 and Cpk = -0.08) and average yield is 94.5% (lower than the 95% standard set by the company). The Six Sigma concept is applied aiming at increasing yield and reducing variation of this process. This approach is suitable since it provides a systematic guideline with five improvement phases (DMAIC) to effectively tackle the problem and find the appropriate parameter settings of the process. Under the new parameter settings, the process yield variation is reduced to range between 96.5% - 98.5% (S.D. = 0.525 and Cpk = 1.83) and the average yield is increased to 97.5% (higher than the 95% standard set by the company).

  15. Enhancing Reactivity in Structural Energetic Materials

    Science.gov (United States)

    Glumac, Nick

    2017-06-01

    In many structural energetic materials, only a small fraction of the metal oxidizes, and yet this provides a significant boost in the overall energy release of the system. Different methodologies to enhance this reactivity include alloying and geometric modifications of microstructure of the reactive material (RM). In this presentation, we present the results of several years of systematic study of both chemical (alloy) and mechanical (geometry) effects on reactivity for systems with typical charge to case mass ratios. Alloys of aluminum with magnesium and lithium are considered, as these are common alloys in aerospace applications. In terms of geometric modifications, we consider surface texturing, inclusion of dense additives, and inclusion of voids. In all modifications, a measurable influence on output is observed, and this influence is related to the fragment size distribution measured from the observed residue. Support from DTRA is gratefully acknowledged.

  16. Chemical reactivity of the compressed noble gas atoms and their ...

    Indian Academy of Sciences (India)

    Attempts are made to gain insights into the effect of confinement of noble gas atoms on their various reactivity indices. Systems become harder, less polarizable and difficult to excite as the compression increases. Ionization also causes similar effects. A quantum fluid density functional technique is adopted in order to study ...

  17. Design and synthesis of reactive separation systems

    Energy Technology Data Exchange (ETDEWEB)

    Doherty, M.F.

    1992-01-01

    During the last decade there has been a rapid upturn in interest in reactive distillation. The chemical process industry recognizes the favorable economics of carrying out reaction simultaneously with distillation for certain classes of reacting systems, and many new processes have been built based on this technology. Interest is also increasing by academics and software vendors. Systematic design methods for reactive distillation systems have only recently begun to emerge. In this report we survey the available design techniques and point out the contributions made by our group at the University of Massachusetts.

  18. Reactivity descriptors and electron density analysis for ligand ...

    Indian Academy of Sciences (India)

    WINTEC

    1Physical Chemistry Division, National Chemical Laboratory, Pune 411 008. 2Scientific and ... 1. Introduction. The prediction of changes in reactivity and selectivity at particular ...... The diimine part of the bipyridine delocalizes the. Figure 3.

  19. Electron Transfer Reactivity Patterns at Chemically Modified Electrodes: Fundamentals and Application to the Optimization of Redox Recycling Amplification Systems

    Energy Technology Data Exchange (ETDEWEB)

    Bergren, Adam Johan [Iowa State Univ., Ames, IA (United States)

    2006-01-01

    Electroanalytical chemistry is often utilized in chemical analysis and Fundamental studies. Important advances have been made in these areas since the advent of chemically modified electrodes: the coating of an electrode with a chemical film in order to impart desirable, and ideally, predictable properties. These procedures enable the exploitation of unique reactivity patterns. This dissertation presents studies that investigate novel reaction mechanisms at self-assembled monolayers on gold. In particular, a unique electrochemical current amplification scheme is detailed that relies on a selective electrode to enable a reactivity pattern that results in regeneration of the analyte (redox recycling). This regenerating reaction can occur up to 250 times for each analyte molecule, leading to a notable enhancement in the observed current. The requirements of electrode selectivity and the resulting amplification and detection limit improvements are described with respect to the heterogeneous and homogeneous electron transfer rates that characterize the system. These studies revealed that the heterogeneous electrolysis of the analyte should ideally be electrochemically reversible, while that for the regenerating agent should be held to a low level. Moreover, the homogeneous reaction that recycles the analyte should occur at a rapid rate. The physical selectivity mechanism is also detailed with respect to the properties of the electrode and redox probes utilized. It is shown that partitioning of the analyte into/onto the adlayer leads to the extraordinary selectivity of the alkanethiolate monolayer modified electrode. Collectively, these studies enable a thorough understanding of the complex electrode mechanism required for successful redox recycling amplification systems, Finally, in a separate (but related) study, the effect of the akyl chain length on the heterogeneous electron transfer behavior of solution-based redox probes is reported, where an odd-even oscillation

  20. Pattern transfer on large samples using a sub-aperture reactive ion beam

    Energy Technology Data Exchange (ETDEWEB)

    Miessler, Andre; Mill, Agnes; Gerlach, Juergen W.; Arnold, Thomas [Leibniz-Institut fuer Oberflaechenmodifizierung (IOM), Permoserstrasse 15, D-04318 Leipzig (Germany)

    2011-07-01

    In comparison to sole Ar ion beam sputtering Reactive Ion Beam Etching (RIBE) reveals the main advantage of increasing the selectivity for different kind of materials due to chemical contributions during the material removal. Therefore RIBE is qualified to be an excellent candidate for pattern transfer applications. The goal of the present study is to apply a sub-aperture reactive ion beam for pattern transfer on large fused silica samples. Concerning this matter, the etching behavior in the ion beam periphery plays a decisive role. Using CF{sub 4} as reactive gas, XPS measurements of the modified surface exposes impurities like Ni, Fe and Cr, which belongs to chemically eroded material of the plasma pot as well as an accumulation of carbon (up to 40 atomic percent) in the beam periphery, respectively. The substitution of CF{sub 4} by NF{sub 3} as reactive gas reveals a lot of benefits: more stable ion beam conditions in combination with a reduction of the beam size down to a diameter of 5 mm and a reduced amount of the Ni, Fe and Cr contaminations. However, a layer formation of silicon nitride handicaps the chemical contribution of the etching process. These negative side effects influence the transfer of trench structures on quartz by changing the selectivity due to altered chemical reaction of the modified resist layer. Concerning this we investigate the pattern transfer on large fused silica plates using NF{sub 3}-sub-aperture RIBE.

  1. Le Châtelier's conjecture: Measurement of colloidal eigenstresses in chemically reactive materials

    Science.gov (United States)

    Abuhaikal, Muhannad; Ioannidou, Katerina; Petersen, Thomas; Pellenq, Roland J.-M.; Ulm, Franz-Josef

    2018-03-01

    Volume changes in chemically reactive materials, such as hydrating cement, play a critical role in many engineering applications that require precise estimates of stress and pressure developments. But a means to determine bulk volume changes in the absence of other deformation mechanisms related to thermal, pressure and load variations, is still missing. Herein, we present such a measuring devise, and a hybrid experimental-theoretical technique that permits the determination of colloidal eigenstresses. Applied to cementitious materials, it is found that bulk volume changes in saturated cement pastes at constant pressure and temperature conditions result from a competition of repulsive and attractive phenomena that originate from the relative distance of the solid particles - much as Henry Louis Le Châtelier, the father of modern cement science, had conjectured in the late 19th century. Precipitation of hydration products in confined spaces entails a repulsion, whereas the concurrent reduction in interparticle distance entails activation of attractive forces in charged colloidal particles. This cross-over from repulsion to attraction can be viewed as a phase transition between a liquid state (below the solid percolation) and the limit packing of hard spheres, separated by an energy barrier that defines the temperature-dependent eigenstress magnitude.

  2. Towards Tetraradicaloid: The Effect of Fusion Mode on Radical Character and Chemical Reactivity

    KAUST Repository

    Hu, Pan

    2015-12-30

    Open-shell singlet diradicaloids display unique electronic, non-linear optical and magnetic activity and could become novel molecular materials for organic electronics, photonics and spintronics. However, design and synthesis of diradicaloids with a significant polyradical character is a challenging task for chemists. In this article, we report our efforts toward tetraradicaloid system. A series of potential tetraradicaloids by fusion of two p-quinodimethane (p-QDM) units with naphthalene or benzene rings in different modes were synthesized. Their model compounds containing one p-QDM moiety were also prepared and compared. Their ground-state structures, physical properties and chemical reactivity were systematically investigated by various exper-imental methods such as steady-state and transient absorption, two-photon absorption, X-ray crystallographic analysis, electron spin resonance, superconducting quantum interference device and electrochemistry, assisted by density functional theory calculations. It was found that their diradical and tetraradical characters show a clear dependence on the fusion mode. Upon the introducing of more five-membered rings, the diradical characters greatly decrease. This difference can be explained by the pro-aromaticity/anti-aromaticity of the molecules as well as the intramolecular charge transfer. Our comprehensive studies provide a guideline for the design and synthesis of stable open-shell singlet polycyclic hydrocarbons with significant polyradical characters.

  3. Towards Tetraradicaloid: The Effect of Fusion Mode on Radical Character and Chemical Reactivity

    KAUST Repository

    Hu, Pan; Lee, Sangsu; Herng, Tun Seng; Aratani, Naoki; Goncalves, Theo; Qi, Qingbiao; Shi, Xueliang; Yamada, Hiroko; Huang, Kuo-Wei; Ding, Jun; Kim, Dongho; Wu, Jishan

    2015-01-01

    Open-shell singlet diradicaloids display unique electronic, non-linear optical and magnetic activity and could become novel molecular materials for organic electronics, photonics and spintronics. However, design and synthesis of diradicaloids with a significant polyradical character is a challenging task for chemists. In this article, we report our efforts toward tetraradicaloid system. A series of potential tetraradicaloids by fusion of two p-quinodimethane (p-QDM) units with naphthalene or benzene rings in different modes were synthesized. Their model compounds containing one p-QDM moiety were also prepared and compared. Their ground-state structures, physical properties and chemical reactivity were systematically investigated by various exper-imental methods such as steady-state and transient absorption, two-photon absorption, X-ray crystallographic analysis, electron spin resonance, superconducting quantum interference device and electrochemistry, assisted by density functional theory calculations. It was found that their diradical and tetraradical characters show a clear dependence on the fusion mode. Upon the introducing of more five-membered rings, the diradical characters greatly decrease. This difference can be explained by the pro-aromaticity/anti-aromaticity of the molecules as well as the intramolecular charge transfer. Our comprehensive studies provide a guideline for the design and synthesis of stable open-shell singlet polycyclic hydrocarbons with significant polyradical characters.

  4. Reactive modification of polyesters and their blends

    Science.gov (United States)

    Wan, Chen

    2004-12-01

    As part of a broader research effort to investigate the chemical modification of polyesters by reactive processing a low molecular weight (MW) unsaturated polyester (UP) and a higher MW saturated polyester, polyethylene terephthalate (PET), alone or blended with polypropylene (PP) were melt processed in a batch mixer and continuous twin screw extruders. Modification was monitored by on-line rheology and the products were characterized primarily by off-line rheology, morphology and thermal analysis. Efforts were made to establish processing/property relationships and provide an insight of the accompanying structural changes. The overall response of the reactively modified systems was found to be strongly dependent on the component characteristics, blend composition, type and concentrations of reactive additives and processing conditions. The work concluded that UP can be effectively modified through reactive melt processing. Its melt viscosity and MW can be increased through chemical reactions between organic peroxides (POX) and chain unsaturation or between MgO and carboxyl/hydroxyl end groups. Reactive blending of PP/UP blends through peroxide modification gave finer and more uniform morphology than unreacted blends and at a given PP/UP weight ratio more thermoplastic elastomers-like rheological behavior. This is due to the continuously decreasing viscosity ratio of PP/UP towards unity by the competing reactions between POX and the blend components and formation of PP-UP copolymers which serve as in-situ compatibilizers to promote better interfacial adhesion. Kinetics of the competing reactions were analyzed through a developed model. In addition to POX concentration and mixing efficiency, rheology and morphology of UP/PP bends were significantly affected by the addition of inorganic and organic coagents. Addition of coagents such as a difunctional maleimide, MgO and/or an anhydride functionalized PP during reactive blending offers effective means for tailoring

  5. Simulations of reactive transport and precipitation with smoothed particle hydrodynamics

    Science.gov (United States)

    Tartakovsky, Alexandre M.; Meakin, Paul; Scheibe, Timothy D.; Eichler West, Rogene M.

    2007-03-01

    A numerical model based on smoothed particle hydrodynamics (SPH) was developed for reactive transport and mineral precipitation in fractured and porous materials. Because of its Lagrangian particle nature, SPH has several advantages for modeling Navier-Stokes flow and reactive transport including: (1) in a Lagrangian framework there is no non-linear term in the momentum conservation equation, so that accurate solutions can be obtained for momentum dominated flows and; (2) complicated physical and chemical processes such as surface growth due to precipitation/dissolution and chemical reactions are easy to implement. In addition, SPH simulations explicitly conserve mass and linear momentum. The SPH solution of the diffusion equation with fixed and moving reactive solid-fluid boundaries was compared with analytical solutions, Lattice Boltzmann [Q. Kang, D. Zhang, P. Lichtner, I. Tsimpanogiannis, Lattice Boltzmann model for crystal growth from supersaturated solution, Geophysical Research Letters, 31 (2004) L21604] simulations and diffusion limited aggregation (DLA) [P. Meakin, Fractals, scaling and far from equilibrium. Cambridge University Press, Cambridge, UK, 1998] model simulations. To illustrate the capabilities of the model, coupled three-dimensional flow, reactive transport and precipitation in a fracture aperture with a complex geometry were simulated.

  6. Responses of human birch pollen allergen-reactive T cells to chemically modified allergens (allergoids).

    Science.gov (United States)

    Dormann, D; Ebner, C; Jarman, E R; Montermann, E; Kraft, D; Reske-Kunz, A B

    1998-11-01

    Allergoids are widely used in specific immunotherapy for the treatment of IgE-mediated allergic diseases. The aim of this study was to analyse whether a modification of birch pollen allergens with formaldehyde affects the availability of T-cell epitopes. Efficient modification of the allergens was verified by determining IgE and IgG binding activity using ELISA inhibition tests. T-cell responses to birch pollen allergoids were analysed in polyclonal systems, using peripheral blood mononuclear cells (PBMC) of five birch pollen-allergic individuals, as well as birch pollen extract-reactive T-cell lines (TCL), established from the peripheral blood of 14 birch pollen-allergic donors. To determine whether the modification of natural (n)Bet v 1 with formaldehyde or maleic anhydride results in epitope-specific changes in T-cell reactivities, 22 Bet v 1-specific T-cell clones (TCC), established from nine additional birch pollen-allergic individuals, were tested for their reactivity with these products. The majority of PBMC and TCL showed a reduced response to the birch pollen extract allergoid. Bet v 1-specific TCC could be divided into allergoid-reactive and -non-reactive TCC. No simple correlation between possible modification sites of formaldehyde in the respective T-cell epitopes and the stimulatory potential of the allergoid was observed. Mechanisms of suppression or of anergy induction were excluded as an explanation for the non-reactivity of representative TCC. All TCC could be stimulated by maleylated and unmodified nBet v 1 to a similar extent. These results demonstrate differences in the availability of T-cell epitopes between allergoids and unmodified allergens, which are most likely due to structural changes within the allergen molecule.

  7. Chemical reagent and process for refuse disposal

    International Nuclear Information System (INIS)

    Somerville, R.B.; Fan, L.T.

    1989-01-01

    A process for treating refuse by mixing them with a reactive chemical and a puzzolana-type material. Said chemical includes a retarding agent which modifies the viscosity and an accelerating agent. (author)

  8. Molecular Electron Density Theory: A Modern View of Reactivity in Organic Chemistry

    OpenAIRE

    Luis R. Domingo

    2016-01-01

    A new theory for the study of the reactivity in Organic Chemistry, named Molecular Electron Density Theory (MEDT), is proposed herein. MEDT is based on the idea that while the electron density distribution at the ground state is responsible for physical and chemical molecular properties, as proposed by the Density Functional Theory (DFT), the capability for changes in electron density is responsible for molecular reactivity. Within MEDT, the reactivity in Organic Chemistry is studied through ...

  9. NHS-Esters As Versatile Reactivity-Based Probes for Mapping Proteome-Wide Ligandable Hotspots.

    Science.gov (United States)

    Ward, Carl C; Kleinman, Jordan I; Nomura, Daniel K

    2017-06-16

    Most of the proteome is considered undruggable, oftentimes hindering translational efforts for drug discovery. Identifying previously unknown druggable hotspots in proteins would enable strategies for pharmacologically interrogating these sites with small molecules. Activity-based protein profiling (ABPP) has arisen as a powerful chemoproteomic strategy that uses reactivity-based chemical probes to map reactive, functional, and ligandable hotspots in complex proteomes, which has enabled inhibitor discovery against various therapeutic protein targets. Here, we report an alkyne-functionalized N-hydroxysuccinimide-ester (NHS-ester) as a versatile reactivity-based probe for mapping the reactivity of a wide range of nucleophilic ligandable hotspots, including lysines, serines, threonines, and tyrosines, encompassing active sites, allosteric sites, post-translational modification sites, protein interaction sites, and previously uncharacterized potential binding sites. Surprisingly, we also show that fragment-based NHS-ester ligands can be made to confer selectivity for specific lysine hotspots on specific targets including Dpyd, Aldh2, and Gstt1. We thus put forth NHS-esters as promising reactivity-based probes and chemical scaffolds for covalent ligand discovery.

  10. Reactivity measurement in estimation of benzoquinone and benzoquinone derivatives’ allergenicity

    International Nuclear Information System (INIS)

    Mbiya, Wilbes; Chipinda, Itai; Simoyi, Reuben H.; Siegel, Paul D.

    2016-01-01

    Benzoquinone (BQ) and benzoquinone derivatives (BQD) are used in the production of dyes and cosmetics. While BQ, an extreme skin sensitizer, is an electrophile known to covalently modify proteins via Michael Addition (MA) reaction whilst halogen substituted BQD undergo nucleophilic vinylic substitution (SNV) mechanism onto amine and thiol moieties on proteins, the allergenic effects of adding substituents on BQ have not been reported. The effects of inserting substituents on the BQ ring has not been studied in animal assays. However, mandated reduction/elimination of animals used in cosmetics testing in Europe has led to an increased need for alternatives for the prediction of skin sensitization potential. Electron withdrawing and electron donating substituents on BQ were assessed for effects on BQ reactivity toward nitrobenzene thiol (NBT). The NBT binding studies demonstrated that addition of EWG to BQ as exemplified by the chlorine substituted BQDs increased reactivity while addition of EDG as in the methyl substituted BQDs reduced reactivity. BQ and BQD skin allerginicity was evaluated in the murine local lymph node assay (LLNA). BQD with electron withdrawing groups had the highest chemical potency followed by unsubstituted BQ and the least potent were the BQD with electron donating groups. The BQD results demonstrate the impact of inductive effects on both BQ reactivity and allergenicity, and suggest the potential utility of chemical reactivity data for electrophilic allergen identification and potency ranking.

  11. Reactivity measurement in estimation of benzoquinone and benzoquinone derivatives’ allergenicity

    Science.gov (United States)

    Mbiya, Wilbes; Chipinda, Itai; Simoyi, Reuben H.; Siegel, Paul D.

    2015-01-01

    Benzoquinone (BQ) and benzoquinone derivatives (BQD) are used in the production of dyes and cosmetics. While BQ, an extreme skin sensitizer, is an electrophile known to covalently modify proteins via Michael Addition (MA) reaction whilst halogen substituted BQD undergo nucleophilic vinylic substitution (SNV) mechanism onto amine and thiol moieties on proteins, the allergenic effects of adding substituents on BQ have not been reported. The effects of inserting substituents on the BQ ring has not been studied in animal assays. However, mandated reduction/elimination of animals used in cosmetics testing in Europe has led to an increased need for alternatives for the prediction of skin sensitization potential. Electron withdrawing and electron donating substituents on BQ were assessed for effects on BQ reactivity toward nitrobenzene thiol (NBT). The NBT binding studies demonstrated that addition of EWG to BQ as exemplified by the chlorine substituted BQDs increased reactivity while addition of EDG as in the methyl substituted BQDs reduced reactivity. BQ and BQD skin allerginicity was evaluated in the murine local lymph node assay (LLNA). BQD with electron withdrawing groups had the highest chemical potency followed by unsubstituted BQ and the least potent were the BQD with electron donating groups. The BQD results demonstrate the impact of inductive effects on both BQ reactivity and allergenicity, and suggest the potential utility of chemical reactivity data for electrophilic allergen identification and potency ranking. PMID:26612505

  12. Influence of crystal defects on the chemical reactivity of recoil atoms in oxygen-containing chromium compounds

    International Nuclear Information System (INIS)

    Costea, T.

    1969-01-01

    The influence of crystal defects on the chemical reactivity of recoil atoms produced by the reaction 50 Cr (n,γ) 51 Cr in oxygen-containing chromium compounds has been studied. Three methods have been used to introduce the defects: doping (K 2 CrO 4 doped with BaCrO 4 ), irradiation by ionizing radiation (K 2 CrO 4 irradiated in the presence of Li 2 CO 3 ) and non-stoichiometry (the semi-conducting oxides of the CrO 3 -Cr 2 O 3 series). The thermal annealing kinetics of the irradiated samples have been determined, and the activation energy has been calculated. In all cases it has been observed that there is a decrease in the activation energy for thermal annealing in the presence of the defects. In order to explain the annealing process, an electronic mechanism has been proposed based on the interaction between the recoil species and the charge-carriers (holes or electrons). (author) [fr

  13. Nasal hyper-reactivity is a common feature in both allergic and nonallergic rhinitis.

    Science.gov (United States)

    Segboer, C L; Holland, C T; Reinartz, S M; Terreehorst, I; Gevorgyan, A; Hellings, P W; van Drunen, C M; Fokkens, W J

    2013-11-01

    Nasal hyper-reactivity is an increased sensitivity of the nasal mucosa to various nonspecific stimuli. Both allergic rhinitis (AR) and nonallergic rhinitis (NAR) patients can elicit nasal hyper-reactivity symptoms. Differences in the prevalence or type of nasal hyper-reactivity in AR and NAR patients are largely unknown. In this study, we quantitatively and qualitatively assessed nasal hyper-reactivity in AR and NAR. In the first part, an analysis of a prospectively collected database was performed to reveal patient-reported symptoms of hyper-reactivity. In the second part, cold dry air provocation (CDA) was performed as a hyper-reactivity measure in AR and NAR patients and healthy controls, and symptoms scores, nasal secretions and peak nasal inspiratory flow were measured. Comparisons were made between AR and NAR patients in both studies. The database analysis revealed high hyper-reactivity prevalence in AR (63.4%) and NAR (66.9%). There were no differences between AR and NAR in terms of the number or type of hyper-reactivity stimuli. Hyper-reactivity to physical stimuli did not exclude a response to chemical stimuli, or vice versa. CDA provocation resulted in a significant increase in rhinitis symptoms and the amount of nasal secretions in AR and NAR patients, but not in controls. We found no quantitative or qualitative differences in nasal hyper-reactivity between AR and NAR patients. It is not possible to differentiate NAR subpopulations based on physical or chemical stimuli. © 2013 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

  14. Force-induced chemical reactions on the metal centre in a single metalloprotein molecule

    Science.gov (United States)

    Zheng, Peng; Arantes, Guilherme M.; Field, Martin J.; Li, Hongbin

    2015-01-01

    Metalloproteins play indispensable roles in biology owing to the versatile chemical reactivity of metal centres. However, studying their reactivity in many metalloproteins is challenging, as protein three-dimensional structure encloses labile metal centres, thus limiting their access to reactants and impeding direct measurements. Here we demonstrate the use of single-molecule atomic force microscopy to induce partial unfolding to expose metal centres in metalloproteins to aqueous solution, thus allowing for studying their chemical reactivity in aqueous solution for the first time. As a proof-of-principle, we demonstrate two chemical reactions for the FeS4 centre in rubredoxin: electrophilic protonation and nucleophilic ligand substitution. Our results show that protonation and ligand substitution result in mechanical destabilization of the FeS4 centre. Quantum chemical calculations corroborated experimental results and revealed detailed reaction mechanisms. We anticipate that this novel approach will provide insights into chemical reactivity of metal centres in metalloproteins under biologically more relevant conditions. PMID:26108369

  15. Novel Semi-Direct OH Reactivity (kOH) Measurements by Chemical Ionization Mass Spectrometry during a Chamber Instrument Comparison Campaign and Continuous Ambient Air Sampling at a Central European GAW Station

    Science.gov (United States)

    Muller, J.; Kubistin, D.; Elste, T.; Plass-Duelmer, C.; Claude, A.; Englert, J.; Holla, R.; Fuchs, H.; Hofzumahaus, A.; Holland, F.; Novelli, A.; Tillmann, R.; Wegener, R.; Rohrer, F.; Yu, Z.; Bohn, B.; Williams, J.; Pfannerstill, E.; Edtbauer, A.; Kluepfel, T.

    2016-12-01

    Total OH reactivity (kOH) has been recognized as a useful measure to gauge the potential atmospheric oxidation capacity and a few different in-situ measurement techniques have been developed over the last 15 years. Here results are presented from a novel semi-direct method developed by the German Weather Service (DWD) utilizing a chemical ionization mass spectrometer (CIMS). Recently in April 2016, the CIMS system participated in a half-blind kOH instrument comparison campaign at the Forschungszentrum Jülich (FZJ) SAPHIR chamber. Experiments provided controlled conditions with a range of different VOC mixtures and varying NOx levels, representing environments dominated by biogenic or urban emissions. Alongside CIMS, kOH was also measured by systems using the comparative reactivity method (CRM) and the pump-probe technique with OH detection. The intercomparison revealed a good performance of CIMS at lower OH reactivities (0-15 s-1), a range for which the instrumental set up was optimized. Limitations of the CIMS system consist of an upper limit for kOH detection and the need for applying a chemical correction function as a result of instrument-internal HOx recycling. Findings and instrument parameters obtained from the FZJ SAPHIR campaign and flow tube experiments are then applied to ambient air kOH measurements at the Meteorological Observatory Hohenpeissenberg (MOHp), Germany. The CIMS instrument is used there for long-term measurements of OH, H2SO4, ROx and kOH. Here, we show ambient air kOH measurements, interpreted in conjunction with volatile organic compounds (VOC) and inorganic trace gases also measured at the GAW station Hohenpeissenberg. These observations provide a unique dataset to investigate turnover rates and seasonal cycles of reactive trace gases, i.e. sources that make up total OH reactivity in this central European, rural setting.

  16. Heterogeneously catalyzed reactive extraction for biomass valorization into chemicals and fuels

    NARCIS (Netherlands)

    Ordomskiy, V.; Khodakov, A.Y.; Nijhuis, T.A.; Schouten, J.C.

    2015-01-01

    This paper focuses on the heterogeneously catalyzed reactive extraction and separation in reaction steps in organic and aqueous phases during the transformation of biomass derived products. Two approaches are demonstrated for decomposing and preserving routes for biomass transformation into valuable

  17. Chemical Safety Alert: Safe Storage and Handling of Swimming Pool Chemicals

    Science.gov (United States)

    Hazards of pool water treatment and maintenance chemicals (e.g., chlorine), and the protective measures pool owners should take to prevent fires, toxic vapor releases, and injuries. Triggered by improper wetting, mixing, or self-reactivity over time.

  18. Inactivation of Escherichia coli on blueberries using cold plasma with chemical augmentation inside a partial vacuum

    Science.gov (United States)

    Justification: The mechanism by which cold plasma inactivates pathogens is through the production of free reactive chemical species. Unfortunately, the most reactive chemical species have the shortest half-life. In a vacuum their half-life is believed to be prolonged. Additionally, these reactive sp...

  19. Evaluation of incremental reactivity and its uncertainty in Southern California.

    Science.gov (United States)

    Martien, Philip T; Harley, Robert A; Milford, Jana B; Russell, Armistead G

    2003-04-15

    The incremental reactivity (IR) and relative incremental reactivity (RIR) of carbon monoxide and 30 individual volatile organic compounds (VOC) were estimated for the South Coast Air Basin using two photochemical air quality models: a 3-D, grid-based model and a vertically resolved trajectory model. Both models include an extended version of the SAPRC99 chemical mechanism. For the 3-D modeling, the decoupled direct method (DDM-3D) was used to assess reactivities. The trajectory model was applied to estimate uncertainties in reactivities due to uncertainties in chemical rate parameters, deposition parameters, and emission rates using Monte Carlo analysis with Latin hypercube sampling. For most VOC, RIRs were found to be consistent in rankings with those produced by Carter using a box model. However, 3-D simulations show that coastal regions, upwind of most of the emissions, have comparatively low IR but higher RIR than predicted by box models for C4-C5 alkenes and carbonyls that initiate the production of HOx radicals. Biogenic VOC emissions were found to have a lower RIR than predicted by box model estimates, because emissions of these VOC were mostly downwind of the areas of primary ozone production. Uncertainties in RIR of individual VOC were found to be dominated by uncertainties in the rate parameters of their primary oxidation reactions. The coefficient of variation (COV) of most RIR values ranged from 20% to 30%, whereas the COV of absolute incremental reactivity ranged from about 30% to 40%. In general, uncertainty and variability both decreased when relative rather than absolute reactivity metrics were used.

  20. 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

  1. Density functional theory and surface reactivity study of bimetallic AgnYm (n+m = 10) clusters

    Science.gov (United States)

    Hussain, Riaz; Hussain, Abdullah Ijaz; Chatha, Shahzad Ali Shahid; Hussain, Riaz; Hanif, Usman; Ayub, Khurshid

    2018-06-01

    Density functional theory calculations have been performed on pure silver (Agn), yttrium (Ym) and bimetallic silver yttrium clusters AgnYm (n + m = 2-10) for reactivity descriptors in order to realize sites for nucleophilic and electrophilic attack. The reactivity descriptors of the clusters, studied as a function of cluster size and shape, reveal the presence of different type of reactive sites in a cluster. The size and shape of the pure silver, yttrium and bimetallic silver yttrium cluster (n = 2-10) strongly influences the number and position of active sites for an electrophilic and/or nucleophilic attack. The trends of reactivities through reactivity descriptors are confirmed through comparison with experimental data for CO binding with silver clusters. Moreover, the adsorption of CO on bimetallic silver yttrium clusters is also evaluated. The trends of binding energies support the reactivity descriptors values. Doping of pure cluster with the other element also influence the hardness, softness and chemical reactivity of the clusters. The softness increases as we increase the number of silver atoms in the cluster, whereas the hardness decreases. The chemical reactivity increases with silver doping whereas it decreases by increasing yttrium concentration. Silver atoms are nucleophilic in small clusters but changed to electrophilic in large clusters.

  2. Pattern transfer on fused silica samples using sub-aperture reactive ion beam etching

    Energy Technology Data Exchange (ETDEWEB)

    Miessler, Andre; Arnold, Thomas [Leibniz-Institut fuer Oberflaechenmodifizierung (IOM), Permoserstrasse 15, D-04318 Leipzig (Germany)

    2012-07-01

    In comparison to sole Ar ion beam sputtering Reactive Ion Beam Etching (RIBE) reveals the main advantage of increasing the selectivity for different kind of materials due to chemical contributions during the material removal. Therefore RIBE is qualified to be an excellent candidate for pattern transfer applications. The goal of the present study is to apply a sub-aperture reactive ion beam for pattern transfer on large fused silica samples. Concerning this matter, the etching behavior in the ion beam periphery plays a decisive role. Using a Kaufman-typed ion source with NF{sub 3} as reactive gas, XPS measurements of the modified surface exposes impurities like Ni, Fe and Cr, which belongs to chemically eroded material of the plasma pot and a layer formation of silicon nitride, handicaps the etching process mainly in the beam periphery where the sputtering contribution decrease. These side effects influence the pattern transfer of trench structures, produced in AZ MIR 701 photoresist by lithography on a 2'' fused silica plate, by changing the selectivity due to modified chemical reactions of the resist layer. Concerning this we investigate a RF-Ion source for sub aperture reactive ion beam applications and finally we examine the pattern transfer on large fused silica plates using NF{sub 3}-sub-aperture RIBE.

  3. Intra-/inter-laboratory validation study on reactive oxygen species assay for chemical photosafety evaluation using two different solar simulators.

    Science.gov (United States)

    Onoue, Satomi; Hosoi, Kazuhiro; Toda, Tsuguto; Takagi, Hironori; Osaki, Naoto; Matsumoto, Yasuhiro; Kawakami, Satoru; Wakuri, Shinobu; Iwase, Yumiko; Yamamoto, Toshinobu; Nakamura, Kazuichi; Ohno, Yasuo; Kojima, Hajime

    2014-06-01

    A previous multi-center validation study demonstrated high transferability and reliability of reactive oxygen species (ROS) assay for photosafety evaluation. The present validation study was undertaken to verify further the applicability of different solar simulators and assay performance. In 7 participating laboratories, 2 standards and 42 coded chemicals, including 23 phototoxins and 19 non-phototoxic drugs/chemicals, were assessed by the ROS assay using two different solar simulators (Atlas Suntest CPS series, 3 labs; and Seric SXL-2500V2, 4 labs). Irradiation conditions could be optimized using quinine and sulisobenzone as positive and negative standards to offer consistent assay outcomes. In both solar simulators, the intra- and inter-day precisions (coefficient of variation; CV) for quinine were found to be below 10%. The inter-laboratory CV for quinine averaged 15.4% (Atlas Suntest CPS) and 13.2% (Seric SXL-2500V2) for singlet oxygen and 17.0% (Atlas Suntest CPS) and 7.1% (Seric SXL-2500V2) for superoxide, suggesting high inter-laboratory reproducibility even though different solar simulators were employed for the ROS assay. In the ROS assay on 42 coded chemicals, some chemicals (ca. 19-29%) were unevaluable because of limited solubility and spectral interference. Although several false positives appeared with positive predictivity of ca. 76-92% (Atlas Suntest CPS) and ca. 75-84% (Seric SXL-2500V2), there were no false negative predictions in both solar simulators. A multi-center validation study on the ROS assay demonstrated satisfactory transferability, accuracy, precision, and predictivity, as well as the availability of other solar simulators. Copyright © 2013 Elsevier Ltd. All rights reserved.

  4. New Fukui, dual and hyper-dual kernels as bond reactivity descriptors.

    Science.gov (United States)

    Franco-Pérez, Marco; Polanco-Ramírez, Carlos-A; Ayers, Paul W; Gázquez, José L; Vela, Alberto

    2017-06-21

    We define three new linear response indices with promising applications for bond reactivity using the mathematical framework of τ-CRT (finite temperature chemical reactivity theory). The τ-Fukui kernel is defined as the ratio between the fluctuations of the average electron density at two different points in the space and the fluctuations in the average electron number and is designed to integrate to the finite-temperature definition of the electronic Fukui function. When this kernel is condensed, it can be interpreted as a site-reactivity descriptor of the boundary region between two atoms. The τ-dual kernel corresponds to the first order response of the Fukui kernel and is designed to integrate to the finite temperature definition of the dual descriptor; it indicates the ambiphilic reactivity of a specific bond and enriches the traditional dual descriptor by allowing one to distinguish between the electron-accepting and electron-donating processes. Finally, the τ-hyper dual kernel is defined as the second-order derivative of the Fukui kernel and is proposed as a measure of the strength of ambiphilic bonding interactions. Although these quantities have never been proposed, our results for the τ-Fukui kernel and for τ-dual kernel can be derived in zero-temperature formulation of the chemical reactivity theory with, among other things, the widely-used parabolic interpolation model.

  5. Reactive Nanocomposites for Controllable Adhesive Debonding

    Science.gov (United States)

    2011-08-01

    technologies include shape memory alloy (SMA)-based approach, a chemical foaming agent (CFA) approach, and a reactive nanocomposite (RNC) approach. SMA...anofoil (a) Component 1 Thermoset Adhesive Component 2 Nano-coating (b) Figure 2. Debonding approach where (a) freestanding...J. Controlled Adhesive Debonding of RAH-66 Comanche Chines Using Shape Memory Alloys ; ARL-TR-2937; U.S. Army Research Laboratory: Aberdeen Proving

  6. Structure, reactivity, and biological properties of hidantoines; Estrutura, reatividade e propriedades biologicas de hidantoinas

    Energy Technology Data Exchange (ETDEWEB)

    Oliveira, Silvania Maria de; Silva, Joao Bosco Paraiso da [Universidade Federal de Pernambuco (UFPE), Recife, PE (Brazil). Dept. de Quimica Fundamental]. E-mail: paraiso@ufpe.br; Hernandes, Marcelo Zaldini [Universidade Federal de Pernambuco (UFPE), Recife, PE (Brazil). Dept. de Ciencias Farmaceuticas; Lima, Maria do Carmo Alves de; Galdino, Suely Lins; Pitta, Ivan da Rocha [Universidade Federal de Pernambuco (UFPE), Recife, PE (Brazil). Dept. de Antibioticos

    2008-07-01

    Hydantoin (imidazolidine-2,4-dione) is a 2,4-diketotetrahydroimidazole discovered by Baeyer in 1861. Thiohydantoins and derivatives were prepared, having chemical properties similar to the corresponding carbonyl compounds. Some biological activities (antimicrobial, anticonvulsant, schistosomicidal) are attributed to the chemical reactivity and consequent affinity of hydantoinic rings towards biomacromolecules. Therefore, knowledge about the chemistry of hydantoins has increased enormously. In this review, we present important aspects such as reactivity of hydantoins, acidity of hydantoins, spectroscopy and crystallographic properties, and biological activities of hydantoin and its derivatives. (author)

  7. 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 ...

  8. Using laboratory flow experiments and reactive chemical transport modeling for designing waterflooding of the Agua Fria Reservoir, Poza Rica-Altamira Field, Mexico

    Energy Technology Data Exchange (ETDEWEB)

    Birkle, P.; Pruess, K.; Xu, T.; Figueroa, R.A. Hernandez; Lopez, M. Diaz; Lopez, E. Contreras

    2008-10-01

    Waterflooding for enhanced oil recovery requires that injected waters must be chemically compatible with connate reservoir waters, in order to avoid mineral dissolution-and-precipitation cycles that could seriously degrade formation permeability and injectivity. Formation plugging is a concern especially in reservoirs with a large content of carbonates, such as calcite and dolomite, as such minerals typically react rapidly with an aqueous phase, and have strongly temperature-dependent solubility. Clay swelling can also pose problems. During a preliminary waterflooding pilot project, the Poza Rica-Altamira oil field, bordering the Gulf coast in the eastern part of Mexico, experienced injectivity loss after five months of reinjection of formation waters into well AF-847 in 1999. Acidizing with HCl restored injectivity. We report on laboratory experiments and reactive chemistry modeling studies that were undertaken in preparation for long-term waterflooding at Agua Frma. Using analogous core plugs obtained from the same reservoir interval, laboratory coreflood experiments were conducted to examine sensitivity of mineral dissolution and precipitation effects to water composition. Native reservoir water, chemically altered waters, and distilled water were used, and temporal changes in core permeability, mineral abundances and aqueous concentrations of solutes were monitored. The experiments were simulated with the multi-phase, nonisothermal reactive transport code TOUGHREACT, and reasonable to good agreement was obtained for changes in solute concentrations. Clay swelling caused an additional impact on permeability behavior during coreflood experiments, whereas the modeled permeability depends exclusively on chemical processes. TOUGHREACT was then used for reservoir-scale simulation of injecting ambient-temperature water (30 C, 86 F) into a reservoir with initial temperature of 80 C (176 F). Untreated native reservoir water was found to cause serious porosity and

  9. 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.)

  10. Hardness and softness reactivity kernels within the spin-polarized density-functional theory

    International Nuclear Information System (INIS)

    Chamorro, Eduardo; De Proft, Frank; Geerlings, Paul

    2005-01-01

    Generalized hardness and softness reactivity kernels are defined within a spin-polarized density-functional theory (SP-DFT) conceptual framework. These quantities constitute the basis for the global, local (i.e., r-position dependent), and nonlocal (i.e., r and r ' -position dependents) indices devoted to the treatment of both charge-transfer and spin-polarization processes in such a reactivity framework. The exact relationships between these descriptors within a SP-DFT framework are derived and the implications for chemical reactivity in such context are outlined

  11. Host-cell reactivation of UV-irradiated and chemically-treated herpes simplex virus-1 by xeroderma pigmentosum, xp heterozygotes and normal skin fibroblasts

    International Nuclear Information System (INIS)

    Selsky, C.A.

    1978-01-01

    The host-cell reactivation of UV-irradiated and N-acetoxy-2-acetylamino-fluorene-treated herpes simplex virus type 1 strain MP was studied in normal and xeroderma pigmentosum human skin fibroblasts. Virus treated with either agent demonstrated lower survival in XP cells from complementation groups A, B, C and D than in normal fibroblasts. The relative reactivation ability of XP cells from the different genetic complementation groups was found to be the same for both irradiated and chemically treated virus. In addition, the inactivation kinetics for virus treated with either agent in the XP variant were comparable to that seen in normal skin fibroblasts. The addition of 2 or 4 mmoles caffeine to the post-infection assay medium had no effect on the inactivation kinetics of virus treated by either agent in the XP variant or in XP cells from the different genetic complementation groups. Treatment of the virus with nitrogen mustard resulted in equivalent survival in normal and XP genetic complementation group D cells. No apparent defect was observed in the ability of XP heterozygous skin fibroblasts to repair virus damaged with up to 100 μg N-acetoxy-2-acetylaminofluorene per ml. These findings indicate that the repair of UV-irradiated and N-acetoxy-2-acetylaminofluorene-treated virus is accomplished by the same pathway or different pathways sharing a common intermediate step and that the excision defect of XP cells plays little if any role in the reactivation of nitrogen mustard treated virus. (Auth.)

  12. TOURGHREACT: A Simulation Program for Non-isothermal Multiphase Reactive Geochemical Transport in Variably Saturated Geologic Media

    OpenAIRE

    Xu, Tianfu; Sonnenthal, Eric; Spycher, Nicolas; Pruess, Karsten

    2004-01-01

    TOUGHREACT is a numerical simulation program for chemically reactive non-isothermal flows of multiphase fluids in porous and fractured media. The program was written in Fortran 77 and developed by introducing reactive geochemistry into the multiphase fluid and heat flow simulator TOUGH2. A variety of subsurface thermo-physical-chemical processes are considered under a wide range of conditions of pressure, temperature, water saturation, ionic strength, and pH and Eh. Interactions between ...

  13. Models for risk assessment of reactive chemicals in aquatic toxicology

    NARCIS (Netherlands)

    Freidig, Andreas Peter

    2000-01-01

    A quantitative structure property relationship (QSPR) for a,b-unsaturated carboxylates (mainly acrylates and methacrylates) was established in chapter 2. Chemical reaction rate constants were measured for 12 different chemicals with three different nucleophiles, namely H 2 O, OH - and glutathione

  14. Application of the Firefly and Luus-Jaakola algorithms in the calculation of a double reactive azeotrope

    Science.gov (United States)

    Mendes Platt, Gustavo; Pinheiro Domingos, Roberto; Oliveira de Andrade, Matheus

    2014-01-01

    The calculation of reactive azeotropes is an important task in the preliminary design and simulation of reactive distillation columns. Classically, homogeneous nonreactive azeotropes are vapor-liquid coexistence conditions where phase compositions are equal. For homogeneous reactive azeotropes, simultaneous phase and chemical equilibria occur concomitantly with equality of compositions (in the Ung-Doherty transformed space). The modeling of reactive azeotrope calculation is represented by a nonlinear algebraic system with phase equilibrium, chemical equilibrium and azeotropy equations. This nonlinear system can exhibit more than one solution, corresponding to a double reactive azeotrope. In a previous paper (Platt et al 2013 J. Phys.: Conf. Ser. 410 012020), we investigated some numerical aspects of the calculation of reactive azeotropes in the isobutene + methanol + methyl-tert-butyl-ether (with two reactive azeotropes) system using two metaheuristics: the Luus-Jaakola adaptive random search and the Firefly algorithm. Here, we use a hybrid structure (stochastic + deterministic) in order to produce accurate results for both azeotropes. After identifying the neighborhood of the reactive azeotrope, the nonlinear algebraic system is solved using Newton's method. The results indicate that using metaheuristics and some techniques devoted to the calculation of multiple minima allows both azeotropic coordinates in this reactive system to be obtains. In this sense, we provide a comprehensive analysis of a useful framework devoted to solving nonlinear systems, particularly in phase equilibrium problems.

  15. Application of the Firefly and Luus–Jaakola algorithms in the calculation of a double reactive azeotrope

    International Nuclear Information System (INIS)

    Platt, Gustavo Mendes; Domingos, Roberto Pinheiro; Andrade, Matheus Oliveira de

    2014-01-01

    The calculation of reactive azeotropes is an important task in the preliminary design and simulation of reactive distillation columns. Classically, homogeneous nonreactive azeotropes are vapor–liquid coexistence conditions where phase compositions are equal. For homogeneous reactive azeotropes, simultaneous phase and chemical equilibria occur concomitantly with equality of compositions (in the Ung–Doherty transformed space). The modeling of reactive azeotrope calculation is represented by a nonlinear algebraic system with phase equilibrium, chemical equilibrium and azeotropy equations. This nonlinear system can exhibit more than one solution, corresponding to a double reactive azeotrope. In a previous paper (Platt et al 2013 J. Phys.: Conf. Ser. 410 012020), we investigated some numerical aspects of the calculation of reactive azeotropes in the isobutene + methanol + methyl-tert-butyl-ether (with two reactive azeotropes) system using two metaheuristics: the Luus–Jaakola adaptive random search and the Firefly algorithm. Here, we use a hybrid structure (stochastic + deterministic) in order to produce accurate results for both azeotropes. After identifying the neighborhood of the reactive azeotrope, the nonlinear algebraic system is solved using Newton's method. The results indicate that using metaheuristics and some techniques devoted to the calculation of multiple minima allows both azeotropic coordinates in this reactive system to be obtains. In this sense, we provide a comprehensive analysis of a useful framework devoted to solving nonlinear systems, particularly in phase equilibrium problems. (paper)

  16. A quantum chemical study of the reactivity of acetaminophen (paracetamol) toxic metabolite N-acetyl-p-benzoquinone imine with deoxyguanosine and glutathione.

    Science.gov (United States)

    Klopčič, Ivana; Poberžnik, Matic; Mavri, Janez; Dolenc, Marija Sollner

    2015-12-05

    Acetaminophen (APAP) forms some reactive metabolites that can react with DNA. APAP is a potentially genotoxic drug and is classified as a Group 3 drug according to International Agency for Research on Cancer (IARC). One of the possible mechanisms of APAP genotoxicity after long term of use is that its reactive quinone imine (QI) metabolite of acetaminophen (NAPQI), can chemically react with DNA after glutathione (GSH) depletion. A quantum chemical study of the reactions between the NAPQI and deoxyguanosine (dG) or GSH was performed. Activation energies (ΔG(ǂ)) for the reactions associated with the 1, 4-Michael addition were calculated on the M062X/6-311++G (d,p) level of theory. We modeled the reaction with dG as a multi-step process. The first step is rate-limiting (ΔG(ǂ) = 26.7 kcal/mol) and consists of formation of a C-N bond between the C3 atom of the QI moiety and the N7 atom of dG. The second step involves proton transfer from the C3 moiety to the nitrogen atom of the QI with ΔG(ǂ) of 13.8 kcal/mol. The depurination reaction that follows has a ΔG(ǂ) of 25.7 kcal/mol. The calculated ΔG(ǂ) for the nucleophilic attack of the deprotonated S atom of GSH on the C3 atom of the NAPQI is 12.9 kcal/mol. Therefore, the QI will react with GSH much faster than with DNA. Our study gives mechanistic insight into the genotoxicity of the APAP metabolite and will be useful for estimating the genotoxic potential of existing drugs with a QI moiety. Our results show that clinical application of APAP is safe, while in the case of severely depleted GSH levels APAP should be administered with caution. Copyright © 2015 Elsevier Ireland Ltd. All rights reserved.

  17. Chemical and Molecular Descriptors for the Reactivity of Amines with CO{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Anita S.; Kitchin, John R.

    2012-10-24

    Amine-based solvents are likely to play an important role in CO{sub 2} capture applications in the future, and the identification of amines with superior performance will facilitate their use in CO{sub 2} capture. While some improvements in performance will be achieved through process modifications, modifying the CO{sub 2} capture performance of an amine also implies in part an ability to modify the reactions between the amine and CO{sub 2} through development of new functionalized amines. We present a computational study of trends in the reactions between CO{sub 2} and functionalized amines with a focus on identifying molecular descriptors that determine trends in reactivity. We examine the formation of bicarbonate and carbamate species on three classes of functionalized amines: alkylamines, alkanolamines, and fluorinated alkylamines including primary, secondary and tertiary amines in each class. These functional groups span electron-withdrawing to donating behavior, hydrogen-bonding, extent of functionalization, and proximity effects of the functional groups. Electron withdrawing groups tend to destabilize CO{sub 2} reaction products, whereas electron-donating groups tend to stabilize CO{sub 2} reaction products. Hydrogen bonding stabilizes CO{sub 2} reaction products. Electronic structure descriptors based on electronegativity were found to describe trends in the bicarbonate formation energy. A chemical correlation was observed between the carbamate formation energy and the carbamic acid formation energy. The local softness on the reacting N in the amine was found to partially explain trends carbamic acid formation energy.

  18. Design and synthesis of reactive separation systems. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Doherty, M.F.

    1992-12-31

    During the last decade there has been a rapid upturn in interest in reactive distillation. The chemical process industry recognizes the favorable economics of carrying out reaction simultaneously with distillation for certain classes of reacting systems, and many new processes have been built based on this technology. Interest is also increasing by academics and software vendors. Systematic design methods for reactive distillation systems have only recently begun to emerge. In this report we survey the available design techniques and point out the contributions made by our group at the University of Massachusetts.

  19. Enhanced formulations for neutralization of chemical, biological and industrial toxants

    Science.gov (United States)

    Tucker, Mark D [Albuqueque, NM

    2008-06-24

    An enhanced formulation and method of making that neutralizes the adverse health effects of both chemical and biological compounds, especially chemical warfare (CW) and biological warfare (BW) agents, and toxic industrial chemicals. The enhanced formulation according to the present invention is non-toxic and non-corrosive and can be delivered by a variety of means and in different phases. The formulation provides solubilizing compounds that serve to effectively render the chemical and biological compounds, particularly CW and BW compounds, susceptible to attack, and at least one reactive compound that serves to attack (and detoxify or kill) the compound. The formulation includes at least one solubilizing agent, a reactive compound, a bleaching activator and water.

  20. DFT reactivity indices in confined many-electron atoms + ∫

    Indian Academy of Sciences (India)

    Unknown

    Functional Theory (DFT) based global descriptors of chemical reactivity for atoms .... interesting due to its utility as a model in the wide variety of applications ... hydrogen atom at Rc = 2⋅0 au is expected to correspond to the energy value of ...

  1. Integration of On-Column Chemical Reactions in Protein Characterization by Liquid Chromatography/Mass Spectrometry: Cross-Path Reactive Chromatography.

    Science.gov (United States)

    Pawlowski, Jake W; Carrick, Ian; Kaltashov, Igor A

    2018-01-16

    Profiling of complex proteins by means of mass spectrometry (MS) frequently requires that certain chemical modifications of their covalent structure (e.g., reduction of disulfide bonds), be carried out prior to the MS or MS/MS analysis. Traditionally, these chemical reactions take place in the off-line mode to allow the excess reagents (the majority of which interfere with the MS measurements and degrade the analytical signal) to be removed from the protein solution prior to MS measurements. In addition to a significant increase in the analysis time, chemical reactions may result in a partial or full loss of the protein if the modifications adversely affect its stability, e.g,, making it prone to aggregation. In this work we present a new approach to solving this problem by carrying out the chemical reactions online using the reactive chromatography scheme on a size exclusion chromatography (SEC) platform with MS detection. This is achieved by using a cross-path reaction scheme, i.e., by delaying the protein injection onto the SEC column (with respect to the injection of the reagent plug containing a disulfide-reducing agent), which allows the chemical reactions to be carried out inside the column for a limited (and precisely controlled) period of time, while the two plugs overlap inside the column. The reduced protein elutes separately from the unconsumed reagents, allowing the signal suppression in ESI to be avoided and enabling sensitive MS detection. The new method is used to measure fucosylation levels of a plasma protein haptoglobin at the whole protein level following online reduction of disulfide-linked tetrameric species to monomeric units. The feasibility of top-down fragmentation of disulfide-containing proteins is also demonstrated using β 2 -microglobulin and a monoclonal antibody (mAb). The new online technique is both robust and versatile, as the cross-path scheme can be readily expanded to include multiple reactions in a single experiment (as

  2. Reactive polymer fused deposition manufacturing

    Science.gov (United States)

    Kunc, Vlastimil; Rios, Orlando; Love, Lonnie J.; Duty, Chad E.; Johs, Alexander

    2017-05-16

    Methods and compositions for additive manufacturing that include reactive or thermosetting polymers, such as urethanes and epoxies. The polymers are melted, partially cross-linked prior to the depositing, deposited to form a component object, solidified, and fully cross-linked. These polymers form networks of chemical bonds that span the deposited layers. Application of a directional electromagnetic field can be applied to aromatic polymers after deposition to align the polymers for improved bonding between the deposited layers.

  3. Synthesis of functional nanocrystallites through reactive thermal plasma processing

    Directory of Open Access Journals (Sweden)

    Takamasa Ishigaki and Ji-Guang Li

    2007-01-01

    Full Text Available A method of synthesizing functional nanostructured powders through reactive thermal plasma processing has been developed. The synthesis of nanosized titanium oxide powders was performed by the oxidation of solid and liquid precursors. Quench gases, either injected from the shoulder of the reactor or injected counter to the plasma plume from the bottom of the reactor, were used to vary the quench rate, and therefore the particle size, of the resultant powders. The experimental results are well supported by numerical analysis on the effects of the quench gas on the flow pattern and temperature field of the thermal plasma as well as on the trajectory and temperature history of the particles. The plasma-synthesized TiO2 nanoparticles showed phase preferences different from those synthesized by conventional wet-chemical processes. Nanosized particles of high crystallinity and nonequilibrium chemical composition were formed in one step via reactive thermal plasma processing.

  4. Oral Administration of the Japanese Traditional Medicine Keishibukuryogan-ka-yokuinin Decreases Reactive Oxygen Metabolites in Rat Plasma: Identification of Chemical Constituents Contributing to Antioxidant Activity

    Directory of Open Access Journals (Sweden)

    Yosuke Matsubara

    2017-02-01

    Full Text Available Insufficient detoxification and/or overproduction of reactive oxygen species (ROS induce cellular and tissue damage, and generated reactive oxygen metabolites become exacerbating factors of dermatitis. Keishibukuryogan-ka-yokuinin (KBGY is a traditional Japanese medicine prescribed to treat dermatitis such as acne vulgaris. Our aim was to verify the antioxidant properties of KBGY, and identify its active constituents by blood pharmacokinetic techniques. Chemical constituents were quantified in extracts of KBGY, crude components, and the plasma of rats treated with a single oral administration of KBGY. Twenty-three KBGY compounds were detected in plasma, including gallic acid, prunasin, paeoniflorin, and azelaic acid, which have been reported to be effective for inflammation. KBGY decreased level of the diacron-reactive oxygen metabolites (d-ROMs in plasma. ROS-scavenging and lipid hydroperoxide (LPO generation assays revealed that gallic acid, 3-O-methylgallic acid, (+-catechin, and lariciresinol possess strong antioxidant activities. Gallic acid was active at a similar concentration to the maximum plasma concentration, therefore, our findings indicate that gallic acid is an important active constituent contributing to the antioxidant effects of KBGY. KBGY and its active constituents may improve redox imbalances induced by oxidative stress as an optional treatment for skin diseases.

  5. Chemical conjugation of cowpea mosaic viruses with reactive HPMA-based polymers

    Czech Academy of Sciences Publication Activity Database

    Laga, Richard; Koňák, Čestmír; Šubr, Vladimír; Ulbrich, Karel; Suthiwangcharoen, N.; Niu, Q.; Wang, Q.

    2010-01-01

    Roč. 21, č. 12 (2010), s. 1669-1685 ISSN 0920-5063 R&D Projects: GA AV ČR KJB400500803; GA ČR GA202/09/2078; GA AV ČR KAN200200651 Institutional research plan: CEZ:AV0Z40500505 Keywords : acylthiazolidine-2-thione reactive groups * bioconjugation * coating Subject RIV: CD - Macromolecular Chemistry Impact factor: 1.842, year: 2010

  6. 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.

  7. Pyridoxylamine reactivity kinetics as an amine based nucleophile for screening electrophilic dermal sensitizers

    Science.gov (United States)

    Chipinda, Itai; Mbiya, Wilbes; Adigun, Risikat Ajibola; Morakinyo, Moshood K.; Law, Brandon F.; Simoyi, Reuben H.; Siegel, Paul D.

    2015-01-01

    Chemical allergens bind directly, or after metabolic or abiotic activation, to endogenous proteins to become allergenic. Assessment of this initial binding has been suggested as a target for development of assays to screen chemicals for their allergenic potential. Recently we reported a nitrobenzenethiol (NBT) based method for screening thiol reactive skin sensitizers, however, amine selective sensitizers are not detected by this assay. In the present study we describe an amine (pyridoxylamine (PDA)) based kinetic assay to complement the NBT assay for identification of amine-selective and non-selective skin sensitizers. UV-Vis spectrophotometry and fluorescence were used to measure PDA reactivity for 57 chemicals including anhydrides, aldehydes, and quinones where reaction rates ranged from 116 to 6.2 × 10−6 M−1 s−1 for extreme to weak sensitizers, respectively. No reactivity towards PDA was observed with the thiol-selective sensitizers, non-sensitizers and prohaptens. The PDA rate constants correlated significantly with their respective murine local lymph node assay (LLNA) threshold EC3 values (R2 = 0.76). The use of PDA serves as a simple, inexpensive amine based method that shows promise as a preliminary screening tool for electrophilic, amine-selective skin sensitizers. PMID:24333919

  8. Biogeochemical processes in a clay formation in situ experiment: Part F - Reactive transport modelling

    Energy Technology Data Exchange (ETDEWEB)

    Tournassat, Christophe, E-mail: c.tournassat@brgm.fr [BRGM, French Geological Survey, Orleans (France); Alt-Epping, Peter [Rock-Water Interaction Group, Institute of Geological Sciences, University of Bern (Switzerland); Gaucher, Eric C. [BRGM, French Geological Survey, Orleans (France); Gimmi, Thomas [Rock-Water Interaction Group, Institute of Geological Sciences, University of Bern (Switzerland)] [Laboratory for Waste Management, Paul Scherrer Institut, Villigen (Switzerland); Leupin, Olivier X. [NAGRA, CH-5430 Wettingen (Switzerland); Wersin, Paul [Gruner Ltd., CH-4020 Basel (Switzerland)

    2011-06-15

    Highlights: > Reactive transport modelling was used to simulate simultaneously solute transport, thermodynamic reactions, ion exchange and biodegradation during an in-situ experiment in a clay-rock formation. > Opalinus clay formation has a high buffering capacity in terms of chemical perturbations caused by bacterial activity. > Buffering capacity is mainly attributed to the carbonate system and to the reactivity of clay surfaces (cation exchange, pH buffering). - Abstract: Reactive transport modelling was used to simulate solute transport, thermodynamic reactions, ion exchange and biodegradation in the Porewater Chemistry (PC) experiment at the Mont Terri Rock Laboratory. Simulations show that the most important chemical processes controlling the fluid composition within the borehole and the surrounding formation during the experiment are ion exchange, biodegradation and dissolution/precipitation reactions involving pyrite and carbonate minerals. In contrast, thermodynamic mineral dissolution/precipitation reactions involving alumo-silicate minerals have little impact on the fluid composition on the time-scale of the experiment. With the accurate description of the initial chemical condition in the formation in combination with kinetic formulations describing the different stages of bacterial activities, it has been possible to reproduce the evolution of important system parameters, such as the pH, redox potential, total organic C, dissolved inorganic C and SO{sub 4} concentration. Leaching of glycerol from the pH-electrode may be the primary source of organic material that initiated bacterial growth, which caused the chemical perturbation in the borehole. Results from these simulations are consistent with data from the over-coring and demonstrate that the Opalinus Clay has a high buffering capacity in terms of chemical perturbations caused by bacterial activity. This buffering capacity can be attributed to the carbonate system as well as to the reactivity of

  9. Thermally activated reaction–diffusion-controlled chemical bulk reactions of gases and solids

    Directory of Open Access Journals (Sweden)

    S. Möller

    2015-01-01

    Full Text Available The chemical kinetics of the reaction of thin films with reactive gases is investigated. The removal of thin films using thermally activated solid–gas to gas reactions is a method to in-situ control deposition inventory in vacuum and plasma vessels. Significant scatter of experimental deposit removal rates at apparently similar conditions was observed in the past, highlighting the need for understanding the underlying processes. A model based on the presence of reactive gas in the films bulk and chemical kinetics is presented. The model describes the diffusion of reactive gas into the film and its chemical interaction with film constituents in the bulk using a stationary reaction–diffusion equation. This yields the reactive gas concentration and reaction rates. Diffusion and reaction rate limitations are depicted in parameter studies. Comparison with literature data on tokamak co-deposit removal results in good agreement of removal rates as a function of pressure, film thickness and temperature.

  10. Runaway chemical reaction exposes community to highly toxic chemicals

    International Nuclear Information System (INIS)

    Kaszniak, Mark; Vorderbrueggen, John

    2008-01-01

    The U.S. Chemical Safety and Hazard Investigation Board (CSB) conducted a comprehensive investigation of a runaway chemical reaction at MFG Chemical (MFG) in Dalton, Georgia on April 12, 2004 that resulted in the uncontrolled release of a large quantity of highly toxic and flammable allyl alcohol and allyl chloride into the community. Five people were hospitalized and 154 people required decontamination and treatment for exposure to the chemicals. This included police officers attempting to evacuate the community and ambulance personnel who responded to 911 calls from residents exposed to the chemicals. This paper presents the findings of the CSB report (U.S. Chemical Safety and Hazard Investigation Board (CSB), Investigation Report: Toxic Chemical Vapor Cloud Release, Report No. 2004-09-I-GA, Washington DC, April 2006) including a discussion on tolling practices; scale-up of batch reaction processes; Process Safety Management (PSM) and Risk Management Plan (RMP) implementation; emergency planning by the company, county and the city; and emergency response and mitigation actions taken during the incident. The reactive chemical testing and atmospheric dispersion modeling conducted by CSB after the incident and recommendations adopted by the Board are also discussed

  11. Relations among several nuclear and electronic density functional reactivity indexes

    Science.gov (United States)

    Torrent-Sucarrat, Miquel; Luis, Josep M.; Duran, Miquel; Toro-Labbé, Alejandro; Solà, Miquel

    2003-11-01

    An expansion of the energy functional in terms of the total number of electrons and the normal coordinates within the canonical ensemble is presented. A comparison of this expansion with the expansion of the energy in terms of the total number of electrons and the external potential leads to new relations among common density functional reactivity descriptors. The formulas obtained provide explicit links between important quantities related to the chemical reactivity of a system. In particular, the relation between the nuclear and the electronic Fukui functions is recovered. The connection between the derivatives of the electronic energy and the nuclear repulsion energy with respect to the external potential offers a proof for the "Quantum Chemical le Chatelier Principle." Finally, the nuclear linear response function is defined and the relation of this function with the electronic linear response function is given.

  12. Comparison of OH reactivity measurements in the atmospheric simulation chamber SAPHIR

    Science.gov (United States)

    Fuchs, Hendrik; Novelli, Anna; Rolletter, Michael; Hofzumahaus, Andreas; Pfannerstill, Eva Y.; Kessel, Stephan; Edtbauer, Achim; Williams, Jonathan; Michoud, Vincent; Dusanter, Sebastien; Locoge, Nadine; Zannoni, Nora; Gros, Valerie; Truong, Francois; Sarda-Esteve, Roland; Cryer, Danny R.; Brumby, Charlotte A.; Whalley, Lisa K.; Stone, Daniel; Seakins, Paul W.; Heard, Dwayne E.; Schoemaecker, Coralie; Blocquet, Marion; Coudert, Sebastien; Batut, Sebastien; Fittschen, Christa; Thames, Alexander B.; Brune, William H.; Ernest, Cheryl; Harder, Hartwig; Muller, Jennifer B. A.; Elste, Thomas; Kubistin, Dagmar; Andres, Stefanie; Bohn, Birger; Hohaus, Thorsten; Holland, Frank; Li, Xin; Rohrer, Franz; Kiendler-Scharr, Astrid; Tillmann, Ralf; Wegener, Robert; Yu, Zhujun; Zou, Qi; Wahner, Andreas

    2017-10-01

    Hydroxyl (OH) radical reactivity (kOH) has been measured for 18 years with different measurement techniques. In order to compare the performances of instruments deployed in the field, two campaigns were conducted performing experiments in the atmospheric simulation chamber SAPHIR at Forschungszentrum Jülich in October 2015 and April 2016. Chemical conditions were chosen either to be representative of the atmosphere or to test potential limitations of instruments. All types of instruments that are currently used for atmospheric measurements were used in one of the two campaigns. The results of these campaigns demonstrate that OH reactivity can be accurately measured for a wide range of atmospherically relevant chemical conditions (e.g. water vapour, nitrogen oxides, various organic compounds) by all instruments. The precision of the measurements (limit of detection CRM) has a higher limit of detection of 2 s-1 at a time resolution of 10 to 15 min. The performances of the instruments were systematically tested by stepwise increasing, for example, the concentrations of carbon monoxide (CO), water vapour or nitric oxide (NO). In further experiments, mixtures of organic reactants were injected into the chamber to simulate urban and forested environments. Overall, the results show that the instruments are capable of measuring OH reactivity in the presence of CO, alkanes, alkenes and aromatic compounds. The transmission efficiency in Teflon inlet lines could have introduced systematic errors in measurements for low-volatile organic compounds in some instruments. CRM instruments exhibited a larger scatter in the data compared to the other instruments. The largest differences to reference measurements or to calculated reactivity were observed by CRM instruments in the presence of terpenes and oxygenated organic compounds (mixing ratio of OH reactants were up to 10 ppbv). In some of these experiments, only a small fraction of the reactivity is detected. The accuracy of CRM

  13. Comparison of OH Reactivity Instruments in the Atmosphere Simulation Chamber SAPHIR.

    Science.gov (United States)

    Fuchs, H.; Novelli, A.; Rolletter, M.; Hofzumahaus, A.; Pfannerstill, E.; Edtbauer, A.; Kessel, S.; Williams, J.; Michoud, V.; Dusanter, S.; Locoge, N.; Zannoni, N.; Gros, V.; Truong, F.; Sarda Esteve, R.; Cryer, D. R.; Brumby, C.; Whalley, L.; Stone, D. J.; Seakins, P. W.; Heard, D. E.; Schoemaecker, C.; Blocquet, M.; Fittschen, C. M.; Thames, A. B.; Coudert, S.; Brune, W. H.; Batut, S.; Tatum Ernest, C.; Harder, H.; Elste, T.; Bohn, B.; Hohaus, T.; Holland, F.; Muller, J. B. A.; Li, X.; Rohrer, F.; Kubistin, D.; Kiendler-Scharr, A.; Tillmann, R.; Andres, S.; Wegener, R.; Yu, Z.; Zou, Q.; Wahner, A.

    2017-12-01

    Two campaigns were conducted performing experiments in the atmospheric simulation chamber SAPHIR at Forschungszentrum Jülich in October 2015 and April 2016 to compare hydroxyl (OH) radical reactivity (kOH) measurements. Chemical conditions were chosen either to be representative of the atmosphere or to test potential limitations of instruments. The results of these campaigns demonstrate that OH reactivity can be accurately measured for a wide range of atmospherically relevant chemical conditions (e.g. water vapor, nitrogen oxides, various organic compounds) by all instruments. The precision of the measurements is higher for instruments directly detecting hydroxyl radicals (OH), whereas the indirect Comparative Reactivity Method (CRM) has a higher limit of detection of 2s-1 at a time resolution of 10 to 15 min. The performances of the instruments were systematically tested by stepwise increasing, for example, the concentrations of carbon monoxide (CO), water vapor or nitric oxide (NO). In further experiments, mixtures of organic reactants were injected in the chamber to simulate urban and forested environments. Overall, the results show that instruments are capable of measuring OH reactivity in the presence of CO, alkanes, alkenes and aromatic compounds. The transmission efficiency in Teflon inlet lines could have introduced systematic errors in measurements for low-volatile organic compounds in some instruments. CRM instruments exhibited a larger scatter in the data compared to the other instruments. The largest differences to the reference were observed by CRM instruments in the presence of terpenes and oxygenated organic compounds. In some of these experiments, only a small fraction of the reactivity is detected. The accuracy of CRM measurements is most likely limited by the corrections that need to be applied in order to account for known effects of, for example, deviations from pseudo-first order conditions, nitrogen oxides or water vapor on the measurement

  14. Advanced Chemical Reduction of Reduced Graphene Oxide and Its Photocatalytic Activity in Degrading Reactive Black 5

    Directory of Open Access Journals (Sweden)

    Christelle Pau Ping Wong

    2015-10-01

    Full Text Available Textile industries consume large volumes of water for dye processing, leading to undesirable toxic dyes in water bodies. Dyestuffs are harmful to human health and aquatic life, and such illnesses as cholera, dysentery, hepatitis A, and hinder the photosynthetic activity of aquatic plants. To overcome this environmental problem, the advanced oxidation process is a promising technique to mineralize a wide range of dyes in water systems. In this work, reduced graphene oxide (rGO was prepared via an advanced chemical reduction route, and its photocatalytic activity was tested by photodegrading Reactive Black 5 (RB5 dye in aqueous solution. rGO was synthesized by dispersing the graphite oxide into the water to form a graphene oxide (GO solution followed by the addition of hydrazine. Graphite oxide was prepared using a modified Hummers’ method by using potassium permanganate and concentrated sulphuric acid. The resulted rGO nanoparticles were characterized using ultraviolet-visible spectrophotometry (UV-Vis, X-ray powder diffraction (XRD, Raman, and Scanning Electron Microscopy (SEM to further investigate their chemical properties. A characteristic peak of rGO-48 h (275 cm−1 was observed in the UV spectrum. Further, the appearance of a broad peak (002, centred at 2θ = 24.1°, in XRD showing that graphene oxide was reduced to rGO. Based on our results, it was found that the resulted rGO-48 h nanoparticles achieved 49% photodecolorization of RB5 under UV irradiation at pH 3 in 60 min. This was attributed to the high and efficient electron transport behaviors of rGO between aromatic regions of rGO and RB5 molecules.

  15. Reactive transport modeling of chemical and isotope data to identify degradation processes of chlorinated ethenes in a diffusion-dominated media

    DEFF Research Database (Denmark)

    Chambon, Julie Claire Claudia; Damgaard, Ida; Jeannottat, Simon

    . Degradation and transport processes of chlorinated ethenes are not well understood in such geological settings, therefore risk assessment and remediation at these sites are particularly challenging. In this work, a combined approach of chemical and isotope analysis on core samples, and reactive transport...... the source zone (between 6 and 12 mbs). Concentrations and stable isotope ratios of the mother compounds and their daughter products, as well as redox parameters, fatty acids and microbial data, were analyzed with discrete sub-sampling along the cores. More samples (each 5 mm) were collected around...... of dechlorination and degradation pathways (biotic reductive dechlorination or abiotic β-elimination with iron minerals) in three core profiles. The model includes diffusion in the matrix, sequential reductive dechlorination, abiotic degradation, isotope fractionation due to degradation and due to diffusion...

  16. Chemical effects of radiation

    International Nuclear Information System (INIS)

    Philips, G.O.

    1986-01-01

    Ionizing radiations initiate chemical changes in materials because of the high energy of their quanta. In water, highly reactive free radicals are produced which can initiate secondary changes of solutes, and in chemical of biological molecules in contact with the water. Free radicals can also be directly produced in irradiated medical products. Their fate can be identified and the molecular basis of radiation inactivation clarified. Methods have now been developed to protect and minimise such radiation damage. (author)

  17. Modelling of reactive fluid transport in deformable porous rocks

    Science.gov (United States)

    Yarushina, V. M.; Podladchikov, Y. Y.

    2009-04-01

    One outstanding challenge in geology today is the formulation of an understanding of the interaction between rocks and fluids. Advances in such knowledge are important for a broad range of geologic settings including partial melting and subsequent migration and emplacement of a melt into upper levels of the crust, or fluid flow during regional metamorphism and metasomatism. Rock-fluid interaction involves heat and mass transfer, deformation, hydrodynamic flow, and chemical reactions, thereby necessitating its consideration as a complex process coupling several simultaneous mechanisms. Deformation, chemical reactions, and fluid flow are coupled processes. Each affects the others. Special effort is required for accurate modelling of the porosity field through time. Mechanical compaction of porous rocks is usually treated under isothermal or isoentropic simplifying assumptions. However, joint consideration of both mechanical compaction and reactive porosity alteration requires somewhat greater than usual care about thermodynamic consistency. Here we consider the modelling of multi-component, multi-phase systems, which is fundamental to the study of fluid-rock interaction. Based on the conservation laws for mass, momentum, and energy in the form adopted in the theory of mixtures, we derive a thermodynamically admissible closed system of equations describing the coupling of heat and mass transfer, chemical reactions, and fluid flow in a deformable solid matrix. Geological environments where reactive transport is important are located at different depths and accordingly have different rheologies. In the near surface, elastic or elastoplastic properties would dominate, whereas viscoplasticity would have a profound effect deeper in the lithosphere. Poorly understood rheologies of heterogeneous porous rocks are derived from well understood processes (i.e., elasticity, viscosity, plastic flow, fracturing, and their combinations) on the microscale by considering a

  18. A Simple Visualization of Double Bond Properties: Chemical Reactivity and UV Fluorescence

    Science.gov (United States)

    Grayson, Scott M.

    2012-01-01

    A simple, easily visualized thin-layer chromatography (TLC) staining experiment is presented that highlights the difference in reactivity between aromatic double bonds and nonaromatic double bonds. Although the stability of aromatic systems is a major theme in organic chemistry, the concept is rarely reinforced "visually" in the undergraduate…

  19. MoMaS reactive transport benchmark using PFLOTRAN

    Science.gov (United States)

    Park, H.

    2017-12-01

    MoMaS benchmark was developed to enhance numerical simulation capability for reactive transport modeling in porous media. The benchmark was published in late September of 2009; it is not taken from a real chemical system, but realistic and numerically challenging tests. PFLOTRAN is a state-of-art massively parallel subsurface flow and reactive transport code that is being used in multiple nuclear waste repository projects at Sandia National Laboratories including Waste Isolation Pilot Plant and Used Fuel Disposition. MoMaS benchmark has three independent tests with easy, medium, and hard chemical complexity. This paper demonstrates how PFLOTRAN is applied to this benchmark exercise and shows results of the easy benchmark test case which includes mixing of aqueous components and surface complexation. Surface complexations consist of monodentate and bidentate reactions which introduces difficulty in defining selectivity coefficient if the reaction applies to a bulk reference volume. The selectivity coefficient becomes porosity dependent for bidentate reaction in heterogeneous porous media. The benchmark is solved by PFLOTRAN with minimal modification to address the issue and unit conversions were made properly to suit PFLOTRAN.

  20. Reactivity study on thermal cracking of vacuum residues

    Science.gov (United States)

    León, A. Y.; Díaz, S. D.; Rodríguez, R. C.; Laverde, D.

    2016-02-01

    This study focused on the process reactivity of thermal cracking of vacuum residues from crude oils mixtures. The thermal cracking experiments were carried out under a nitrogen atmosphere at 120psi between 430 to 500°C for 20 minutes. Temperature conditions were established considering the maximum fractional conversion reported in tests of thermogravimetry performed in the temperature range of 25 to 600°C, with a constant heating rate of 5°C/min and a nitrogen flow rate of 50ml/min. The obtained products were separated in to gases, distillates and coke. The results indicate that the behaviour of thermal reactivity over the chemical composition is most prominent for the vacuum residues with higher content of asphaltenes, aromatics, and resins. Finally some correlations were obtained in order to predict the weight percentage of products from its physical and chemical properties such as CCR, SARA (saturates, aromatics, resins, asphaltenes) and density. The results provide new knowledge of the effect of temperature and the properties of vacuum residues in thermal conversion processes.

  1. Chemical Addressability of Ultraviolet-Inactivated Viral Nanoparticles (VNPs)

    Science.gov (United States)

    Rae, Chris; Koudelka, Kristopher J.; Destito, Giuseppe; Estrada, Mayra N.; Gonzalez, Maria J.; Manchester, Marianne

    2008-01-01

    Background Cowpea Mosaic Virus (CPMV) is increasingly being used as a nanoparticle platform for multivalent display of molecules via chemical bioconjugation to the capsid surface. A growing variety of applications have employed the CPMV multivalent display technology including nanoblock chemistry, in vivo imaging, and materials science. CPMV nanoparticles can be inexpensively produced from experimentally infected cowpea plants at high yields and are extremely stable. Although CPMV has not been shown to replicate in mammalian cells, uptake in mammalian cells does occur in vitro and in vivo. Thus, inactivation of the virus RNA genome is important for biosafety considerations, however the surface characteristics and chemical reactivity of the particles must be maintained in order to preserve chemical and structural functionality. Methodology/Principal Findings Short wave (254 nm) UV irradiation was used to crosslink the RNA genome within intact particles. Lower doses of UV previously reported to inactivate CPMV infectivity inhibited symptoms on inoculated leaves but did not prohibit systemic virus spread in plants, whereas higher doses caused aggregation of the particles and an increase in chemical reactivity further indicating broken particles. Intermediate doses of 2.0–2.5 J/cm2 were shown to maintain particle structure and chemical reactivity, and cellular binding properties were similar to CPMV-WT. Conclusions These studies demonstrate that it is possible to inactivate CPMV infectivity while maintaining particle structure and function, thus paving the way for further development of CPMV nanoparticles for in vivo applications. PMID:18830402

  2. Chemical addressability of ultraviolet-inactivated viral nanoparticles (VNPs.

    Directory of Open Access Journals (Sweden)

    Chris Rae

    2008-10-01

    Full Text Available Cowpea Mosaic Virus (CPMV is increasingly being used as a nanoparticle platform for multivalent display of molecules via chemical bioconjugation to the capsid surface. A growing variety of applications have employed the CPMV multivalent display technology including nanoblock chemistry, in vivo imaging, and materials science. CPMV nanoparticles can be inexpensively produced from experimentally infected cowpea plants at high yields and are extremely stable. Although CPMV has not been shown to replicate in mammalian cells, uptake in mammalian cells does occur in vitro and in vivo. Thus, inactivation of the virus RNA genome is important for biosafety considerations, however the surface characteristics and chemical reactivity of the particles must be maintained in order to preserve chemical and structural functionality.Short wave (254 nm UV irradiation was used to crosslink the RNA genome within intact particles. Lower doses of UV previously reported to inactivate CPMV infectivity inhibited symptoms on inoculated leaves but did not prohibit systemic virus spread in plants, whereas higher doses caused aggregation of the particles and an increase in chemical reactivity further indicating broken particles. Intermediate doses of 2.0-2.5 J/cm(2 were shown to maintain particle structure and chemical reactivity, and cellular binding properties were similar to CPMV-WT.These studies demonstrate that it is possible to inactivate CPMV infectivity while maintaining particle structure and function, thus paving the way for further development of CPMV nanoparticles for in vivo applications.

  3. Journal of Chemical Sciences | Indian Academy of Sciences

    Indian Academy of Sciences (India)

    Abstract. The structure and coordination chemistry of boron porphyrin complexes B2OX2 (TYPP) (X = OH, F; Y = Cl, CH3) in connection with its chemical reactivity are analyzed at ab initio density functional theory B3LYP/6-31G∗ and restricted Hartree-Fock RHF/6-31G∗ levels of theory. Global reactivity and local selectivity ...

  4. In-situ high-pressure measurements and detailed numerical predictions of the catalytic reactivity of methane over platinum

    Energy Technology Data Exchange (ETDEWEB)

    Reinke, M.; Mantzaras, I.; Schaeren, R.; Bombach, R.; Inauen, A.; Schenker, S.

    2003-03-01

    The catalytic reactivity of methane over platinum at pressures of up to 14 bar was evaluated with in-situ Raman measurements and detailed numerical predictions from two different heterogeneous chemical reaction schemes. The best agreement to the measurements was achieved with Deutschmann's reaction scheme that yielded the correct trend for the pressure dependence of the catalytic reactivity, although in absolute terms the reactivity was overpredicted. The catalytic reactivity was consistently underpredicted at all pressures with the reaction scheme of Vlachos. (author)

  5. The reactivity meter and core reactivity

    International Nuclear Information System (INIS)

    Siltanen, P.

    1999-01-01

    This paper discussed in depth the point kinetic equations and the characteristics of the point kinetic reactivity meter, particularly for large negative reactivities. From a given input signal representing the neutron flux seen by a detector, the meter computes a value of reactivity in dollars (ρ/β), based on inverse point kinetics. The prompt jump point of view is emphasised. (Author)

  6. Chemical reactivity of precursor materials during synthesis of glasses used for conditioning high-level radioactive waste: Experiments and models

    International Nuclear Information System (INIS)

    Monteiro, A.

    2012-01-01

    The glass used to store high-level radioactive waste is produced by reaction of a solid waste residue and a glassy precursor (glass frit). The waste residue is first dried and calcined (to lose water and nitrogen respectively), then mixed with the glass frit to enable vitrification at high temperature. In order to obtain a good quality glass of constant composition upon cooling, the chemical reactions between the solid precursors must be complete while in the liquid state, to enable incorporation of the radioactive elements into the glassy matrix. The physical and chemical conditions during glass synthesis (e.g. temperature, relative proportions of frit and calcine, amount of radioactive charge) are typically empirically adjusted to obtain a satisfactory final product. The aim of this work is to provide new insights into the chemical and physical interactions that take place during vitrification and to provide data for a mathematical model that has been developed to simulate the chemical reactions. The consequences of the different chemical reactions that involve solid, liquid and gaseous phases are described (thermal effects, changes in crystal morphology and composition, variations in melt properties and structure). In a first series of experiments, a simplified analogue of the calcine (NaNO 3 -Al 2 O 3 ± MoO 3 /Nd 2 O 3 ) has been studied. In a second series of experiments, the simplified calcines have been reacted with a simplified glass frit (SiO 2 -Na 2 O-B 2 O 3 -Al 2 O 3 ) at high temperature. The results show that crystallization of the calcine may take place before interaction with the glass frit, but that the reactivity with the glass at high temperature is a function of the nature and stoichiometry of the crystalline phases which form at low temperature. The results also highlight how the mixing of the starting materials, the physical properties of the frit (viscosity, glass transition temperature) and the Na 2 O/Al 2 O 3 of the calcine but also its

  7. Reactive transport in a partially molten system with binary solid solution

    Science.gov (United States)

    Jordan, J.; Hesse, M. A.

    2017-12-01

    Melt extraction from the Earth's mantle through high-porosity channels is required to explain the composition of the oceanic crust. Feedbacks from reactive melt transport are thought to localize melt into a network of high-porosity channels. Recent studies invoke lithological heterogeneities in the Earth's mantle to seed the localization of partial melts. Therefore, it is necessary to understand the reaction fronts that form as melt flows across the lithological interface of a heterogeneity and the background mantle. Simplified melting models of such systems aide in the interpretation and formulation of larger scale mantle models. Motivated by the aforementioned facts, we present a chromatographic analysis of reactive melt transport across lithological boundaries, using theory for hyperbolic conservation laws. This is an extension of well-known linear trace element chromatography to the coupling of major elements and energy transport. Our analysis allows the prediction of the feedbacks that arise in reactive melt transport due to melting, freezing, dissolution and precipitation for frontal reactions. This study considers the simplified case of a rigid, partially molten porous medium with binary solid solution. As melt traverses a lithological contact-modeled as a Riemann problem-a rich set of features arise, including a reacted zone between an advancing reaction front and partial chemical preservation of the initial contact. Reactive instabilities observed in this study originate at the lithological interface rather than along a chemical gradient as in most studies of mantle dynamics. We present a regime diagram that predicts where reaction fronts become unstable, thereby allowing melt localization into high-porosity channels through reactive instabilities. After constructing the regime diagram, we test the one-dimensional hyperbolic theory against two-dimensional numerical experiments. The one-dimensional hyperbolic theory is sufficient for predicting the

  8. The ionising radiation effect on reactivation of antibiotics

    International Nuclear Information System (INIS)

    Dikij, I.L.; Manskij, A.A.; Krasnopyorova, A.P.

    2002-01-01

    The effect of gamma-radiation on the molecular structure of antibiotics was studied with a view to extending their useful life beyond the current expiration period. The following antibiotics were examined: penicillin, bicillin-3,5, streptomycine, and ampioxe. The samples were irradiated by Co-60 gamma-radiation from a research irradiator. Doses of 0.1, 1, 5, 7, and 10 Gy were applied. The processes were elucidated using the classical method of 2-divisible serial dilutions and IR-spectroscopy. All the measurements were carried out at 300 K. The IR-spectra revealed that the chemical structure of new and old antibiotics is identical; the change in the antibiotic activity is generally a result of deformation of the molecule or change in its conformation; the reactivation process returns the molecule to its previous state and the activity of antibiotic after reactivation meets established standards. Hence, this method can be used for the reactivation of expired antibiotics

  9. Inverse modeling of multicomponent reactive transport through single and dual porosity media

    Science.gov (United States)

    Samper, Javier; Zheng, Liange; Fernández, Ana María; Montenegro, Luis

    2008-06-01

    Compacted bentonite is foreseen as buffer material for high-level radioactive waste in deep geological repositories because it provides hydraulic isolation, chemical stability, and radionuclide sorption. A wide range of laboratory tests were performed within the framework of FEBEX ( Full-scale Engineered Barrier EXperiment) project to characterize buffer properties and develop numerical models for FEBEX bentonite. Here we present inverse single and dual-continuum multicomponent reactive transport models of a long-term permeation test performed on a 2.5 cm long sample of FEBEX bentonite. Initial saline bentonite porewater was flushed with 5.5 pore volumes of fresh granitic water. Water flux and chemical composition of effluent waters were monitored during almost 4 years. The model accounts for solute advection and diffusion and geochemical reactions such as aqueous complexation, acid-base, cation exchange, protonation/deprotonation by surface complexation and dissolution/precipitation of calcite, chalcedony and gypsum. All of these processes are assumed at local equilibrium. Similar to previous studies of bentonite porewater chemistry on batch systems which attest the relevance of protonation/deprotonation on buffering pH, our results confirm that protonation/deprotonation is a key process in maintaining a stable pH under dynamic transport conditions. Breakthrough curves of reactive species are more sensitive to initial porewater concentration than to effective diffusion coefficient. Optimum estimates of initial porewater chemistry of saturated compacted FEBEX bentonite are obtained by solving the inverse problem of multicomponent reactive transport. While the single-continuum model reproduces the trends of measured data for most chemical species, it fails to match properly the long tails of most breakthrough curves. Such limitation is overcome by resorting to a dual-continuum reactive transport model.

  10. Scattering theory and chemical reactions

    International Nuclear Information System (INIS)

    Kuppermann, A.

    1988-01-01

    In this course, scattering theory and chemical reactions are presented including scattering of one particle by a potential, n-particle systems, colinear triatomic molecules and the study of reactive scattering for 3-dimensional triatomic systems. (A.C.A.S.) [pt

  11. Aqueous chemistry of chlorine: chemistry, analysis, and environmental fate of reactive oxidant species

    Energy Technology Data Exchange (ETDEWEB)

    Jolley, R.L.; Carpenter, J.H.

    1982-01-01

    This report reviews (1) the chemistry of chlorine relative to its reactions in fresh, estuarine, and marine waters and the formation of reactive oxidant species; (2) the current status of chemical analysis of reactive chlorine species and chlorine-produced oxidant species relative to analysis of low concentrations (microgram-per-liter range) and determination of accuracy and precision of methods; and (3) the environmental fate of chlorine and chlorine-produced oxidant species.

  12. High Resolution Magic Angle Spinning Nuclear Magnetic Resonance (HRMAS NMR) for Studies of Reactive Fabrics

    Science.gov (United States)

    2015-11-01

    spectroscopy (NMR) Self- decontaminating fabric Reactive fabric...reactions of reagents including chemical weapons on materials like concrete, soil , and sand, as well as reactive polymers.3,4,5,6,7 There are...sample. The rotor and cap can be cleaned by rinsing with solvent or decontamination solution and reused. 12.0 DATA ANALYSIS AND CALCULATIONS 12.1

  13. PERMEABLE REACTIVE BARRIERS FOR IN-SITU TREATMENT OF ARSENIC-CONTAMINATED GROUNDWATER

    Science.gov (United States)

    Laboratory and field research has shown that permeable reactive barriers (PRBs) containing a variety of materials can treat arsenic (As) contaminated groundwater. Sites where these PRBs are located include a mine tailings facility, fertilizer and chemical manufacturing sites, a...

  14. Comparison of OH reactivity measurements in the atmospheric simulation chamber SAPHIR

    Directory of Open Access Journals (Sweden)

    H. Fuchs

    2017-10-01

    Full Text Available Hydroxyl (OH radical reactivity (kOH has been measured for 18 years with different measurement techniques. In order to compare the performances of instruments deployed in the field, two campaigns were conducted performing experiments in the atmospheric simulation chamber SAPHIR at Forschungszentrum Jülich in October 2015 and April 2016. Chemical conditions were chosen either to be representative of the atmosphere or to test potential limitations of instruments. All types of instruments that are currently used for atmospheric measurements were used in one of the two campaigns. The results of these campaigns demonstrate that OH reactivity can be accurately measured for a wide range of atmospherically relevant chemical conditions (e.g. water vapour, nitrogen oxides, various organic compounds by all instruments. The precision of the measurements (limit of detection  < 1 s−1 at a time resolution of 30 s to a few minutes is higher for instruments directly detecting hydroxyl radicals, whereas the indirect comparative reactivity method (CRM has a higher limit of detection of 2 s−1 at a time resolution of 10 to 15 min. The performances of the instruments were systematically tested by stepwise increasing, for example, the concentrations of carbon monoxide (CO, water vapour or nitric oxide (NO. In further experiments, mixtures of organic reactants were injected into the chamber to simulate urban and forested environments. Overall, the results show that the instruments are capable of measuring OH reactivity in the presence of CO, alkanes, alkenes and aromatic compounds. The transmission efficiency in Teflon inlet lines could have introduced systematic errors in measurements for low-volatile organic compounds in some instruments. CRM instruments exhibited a larger scatter in the data compared to the other instruments. The largest differences to reference measurements or to calculated reactivity were observed by CRM instruments in

  15. OH Reactivity Observations during the MAPS-Seoul Campaign: Contrasts between Urban and Suburban Environments

    Science.gov (United States)

    Sanchez, D.; Jeong, D.; Blake, D. R.; Wang, M. D.; Kim, D. S.; Lee, G.; Lee, M.; Jung, J.; Ahn, J.; Cho, G.; Guenther, A. B.; Kim, S.

    2015-12-01

    Direct total OH reactivity was observed in the urban and suburban environments of Seoul, South Korea using a comparative reactivity method (CRM) during the MAPS-Seoul field campaign. In addition, CO, NOx, SO2, ozone, VOCs, aerosol, physical, and chemical parameters were also deployed. By comparing the observed total OH reactivity results with calculated OH reactivity from the trace gas observational datasets, we will evaluate our current status in constraining reactive gases in the urban and suburban environments in the East Asian megacity. Observed urban OH reactivity will be presented in the context of the ability to constrain anthropogenic reactive trace gas emissions. It will then be compared to the observed suburban results from Taehwa Research Forest (located ~ 50 km from the Seoul City Center). Our understanding of reactive trace gases in an environment of high BVOC emissions in a mildly aged anthropogenic influences will be evaluated. Using an observational constrained box model with detailed VOC oxidation schemes (e.g. MCM), we will discuss: 1) what is the amount of missing OH reactivity 2) what are the potential sources of the missing OH reactivity, and 3) what are the implications on regional air quality?

  16. GEOCHEMISTRY OF SUBSURFACE REACTIVE BARRIERS FOR REMEDIATION OF CONTAMINATED GROUND WATER

    Science.gov (United States)

    Reactive barriers that couple subsurface fluid flow with a passive chemical treatment zone are emerging, cost effective approaches for in-situ remediation of contaminated groundwater. Factors such as the build-up of surface precipitates, bio-fouling, and changes in subsurface tr...

  17. Stereodynamics: From elementary processes to macroscopic chemical reactions

    Energy Technology Data Exchange (ETDEWEB)

    Kasai, Toshio [Department of Chemistry, National Taiwan University, Taipei 106, Taiwan (China); Graduate School of Science, Department of Chemistry, Osaka University, Toyonaka, 560-0043 Osaka (Japan); Che, Dock-Chil [Graduate School of Science, Department of Chemistry, Osaka University, Toyonaka, 560-0043 Osaka (Japan); Tsai, Po-Yu [Department of Chemistry, National Taiwan University, Taipei 106, Taiwan (China); Department of Chemistry, National Chung Hsing University, Taichung 402, Taiwan (China); Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei 106, Taiwan (China); Lin, King-Chuen [Department of Chemistry, National Taiwan University, Taipei 106, Taiwan (China); Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei 106, Taiwan (China); Palazzetti, Federico [Scuola Normale Superiore, Pisa (Italy); Dipartimento di Chimica Biologia e Biotecnologie, Università di Perugia, 06123 Perugia (Italy); Aquilanti, Vincenzo [Dipartimento di Chimica Biologia e Biotecnologie, Università di Perugia, 06123 Perugia (Italy); Istituto di Struttura della Materia, Consiglio Nazionale delle Ricerche, Roma (Italy); Instituto de Fisica, Universidade Federal da Bahia, Salvador (Brazil)

    2015-12-31

    This paper aims at discussing new facets on stereodynamical behaviors in chemical reactions, i.e. the effects of molecular orientation and alignment on reactive processes. Further topics on macroscopic processes involving deviations from Arrhenius behavior in the temperature dependence of chemical reactions and chirality effects in collisions are also discussed.

  18. Influence of pyrolysis conditions on the structure and gasification reactivity of biomass chars

    Energy Technology Data Exchange (ETDEWEB)

    E. Cetin; B. Moghtaderi; R. Gupta; T.F. Wall [University of Newcastle, Callaghan, NSW (Australia). Discipline of Chemical Engineering, Faculty of Engineering and Built Environment, School of Engineering

    2004-11-01

    The physical and chemical structure as well as gasification reactivities of chars generated from several biomass species (i.e. pinus radiata, eucalyptus maculata and sugar cane bagasse) were studied to gain insight into the role of heating rate and pressure on the gasification characteristics of biomass chars. Char samples were generated in a suite of reactors including a wire mesh reactor, a tubular reactor, and a drop tube furnace. Scanning electron microscopy analysis, X-ray diffractometry, digital cinematography and surface area analysis were employed to determine the impact of operating conditions on the char structure. The global gasification reactivities of char samples were also determined for a range of pressures between 1 and 20 bar using pressurised thermogravimetric analysis technique. Char reactivities were found to increase with increasing pyrolysis heating rates and decreasing pyrolysis pressure. It was found that under high heating rates the char particles underwent plastic deformation (i.e. melted) developing a structure different to that of the virgin biomass. Pressure was also found to influence the physical and chemical structures of char particles. The difference in the gasification reactivities of biomass chars at pressure was found to correlate well with the effect of pyrolysis pressure on the graphitisation process in the biomass char structure. 29 refs., 18 figs., 2 tabs.

  19. Structure-mechanism-based engineering of chemical regulators targeting distinct pathological factors in Alzheimer's disease.

    Science.gov (United States)

    Beck, Michael W; Derrick, Jeffrey S; Kerr, Richard A; Oh, Shin Bi; Cho, Woo Jong; Lee, Shin Jung C; Ji, Yonghwan; Han, Jiyeon; Tehrani, Zahra Aliakbar; Suh, Nayoung; Kim, Sujeong; Larsen, Scott D; Kim, Kwang S; Lee, Joo-Yong; Ruotolo, Brandon T; Lim, Mi Hee

    2016-10-13

    The absence of effective therapeutics against Alzheimer's disease (AD) is a result of the limited understanding of its multifaceted aetiology. Because of the lack of chemical tools to identify pathological factors, investigations into AD pathogenesis have also been insubstantial. Here we report chemical regulators that demonstrate distinct specificity towards targets linked to AD pathology, including metals, amyloid-β (Aβ), metal-Aβ, reactive oxygen species, and free organic radicals. We obtained these chemical regulators through a rational structure-mechanism-based design strategy. We performed structural variations of small molecules for fine-tuning their electronic properties, such as ionization potentials and mechanistic pathways for reactivity towards different targets. We established in vitro and/or in vivo efficacies of the regulators for modulating their targets' reactivities, ameliorating toxicity, reducing amyloid pathology, and improving cognitive deficits. Our chemical tools show promise for deciphering AD pathogenesis and discovering effective drugs.

  20. Slow Invariant Manifolds in Chemically Reactive Systems

    Science.gov (United States)

    Paolucci, Samuel; Powers, Joseph M.

    2006-11-01

    The scientific design of practical gas phase combustion devices has come to rely on the use of mathematical models which include detailed chemical kinetics. Such models intrinsically admit a wide range of scales which renders their accurate numerical approximation difficult. Over the past decade, rational strategies, such as Intrinsic Low Dimensional Manifolds (ILDM) or Computational Singular Perturbations (CSP), for equilibrating fast time scale events have been successfully developed, though their computation can be challenging and their accuracy in most cases uncertain. Both are approximations to the preferable slow invariant manifold which best describes how the system evolves in the long time limit. Strategies for computing the slow invariant manifold are examined, and results are presented for practical combustion systems.

  1. Thermoset polymers chemo-rheology dedicated to reactive rotational moulding (RRM) understanding and control

    International Nuclear Information System (INIS)

    Viale, J.

    2009-12-01

    This study comes within the scope of New Technology for Energy, particularly for high pressure hydrogen storage. Reactive Rotational Moulding has been identified as an adapted process for hydrogen-tight liners manufacturing. Thus the Reactive Rotational Moulding process has been studied in order to find theoretical tools dedicated to the understanding of such a reactive forming process. Chemical kinetics of four polyurethanes and poly-epoxides reactive systems have been determined on classical isothermal conditions and original aniso-thermal conditions i.e. on temperature ramps. Aniso-thermal conditions have been selected because they corresponds better to real process conditions. Rheological behaviour have also been characterized on two different approaches, an isothermal one and on temperature ramps. In particular, viscosity have been described as a function of heating rate. These physical and chemical results have been compiled in an original state diagram in order to show material properties evolution in a time-temperature space. The whole ex situ characterizations are then managed to described the behavior of the different formulations during the rotational moulding. Moreover they allow to form specific materials and so to widen the range of material to thermoset polymers. Finally, in order to correlate theoretical deduction to real reactive systems evolution, the elaboration of innovating monitoring tool based on ultrasonic analysis has been studied. To begin, polymerization monitoring criteria have been identified and then specific techniques have been set to monitor these criteria in real forming process. (author)

  2. Structure, aromaticity and reactivity of corannulene and its analogues: a conceptual density functional theory and density functional reactivity theory study

    Science.gov (United States)

    Deng, Youer; Yu, Donghai; Cao, Xiaofang; Liu, Lianghong; Rong, Chunying; Lu, Tian; Liu, Shubin

    2018-04-01

    Corannulene is an interesting yet special molecule, which has witnessed widespread applications. It is aromatic, but not planar and the total number of 20 π electrons is in conflict with Hückel's 4n + 2 rule. In this work, we design a series of analogous model systems based on this molecule with the central ring size extended from five members to three to eight members. A number of theoretical and analytical tools available in the literature are employed to systematically examine their structure, aromaticity and reactivity properties. We found that structurally speaking, they change from bowl-like to planar and then to saddle shapes as the central ring size increases from three to eight. From the reactivity perspective, species with five and six-membered-rings in the centre are chemically more stable and less reactive, which are confirmed by the numerical results from aromaticity indexes and quantities from the information-theoretic approach. Overall, our results show that only corannulene and its six-membered-ring, coronene, analogue are aromatic. Even though these two systems are aromatic in nature, they are markedly different in a number of ways in structure, reactivity and other properties. These results should provide with us insights and understanding about the phenomenon of three-dimensional and non-planarity aromaticity.

  3. Chemical gel barriers as low-cost alternative to containment and in situ cleanup of hazardous wastes to protect groundwater

    International Nuclear Information System (INIS)

    1997-01-01

    Chemical gel barriers are being considered as a low-cost alternative for containment and in situ cleanup of hazardous wastes to protect groundwater. Most of the available gels in petroleum application are non-reactive and relative impermeable, providing a physical barriers for all fluids and contaminants. However, other potential systems can be envisioned. These systems could include gels that are chemically reactive and impermeable such that most phase are captured by the barriers but the contaminants could diffuse through the barriers. Another system that is chemically reactive and permeable could have potential applications in selectivity capturing contaminants while allowing water to pass through the barriers. This study focused on chemically reactive and permeable gel barriers. The gels used in experiment are DuPont LUDOX SM colloidal silica gel and Pfizer FLOPAAM 1330S hydrolyzed polyacrylamide (HPAM) gel

  4. Surface characterization after subaperture reactive ion beam etching

    Energy Technology Data Exchange (ETDEWEB)

    Miessler, Andre; Arnold, Thomas; Rauschenbach, Bernd [Leibniz-Institut fuer Oberflaechenmodifizierung (IOM), Leipzig (Germany)

    2010-07-01

    In usual ion beam etching processes using inert gas (Ar, Xe, Kr..) the material removal is determined by physical sputtering effects on the surface. The admixture of suitable gases (CF{sub 4}+O{sub 2}) into the glow discharge of the ion beam source leads to the generation of reactive particles, which are accelerated towards the substrate where they enhance the sputtering process by formation of volatile chemical reaction products. During the last two decades research in Reactive Ion Beam Etching (RIBE) has been done using a broad beam ion source which allows the treatment of smaller samples (diameter sample < diameter beam). Our goal was to apply a sub-aperture Kaufman-type ion source in combination with an applicative movement of the sample with respect to the source, which enables us to etch areas larger than the typical lateral dimensions of the ion beam. Concerning this matter, the etching behavior in the beam periphery plays a decisive role and has to be investigated. We use interferometry to characterize the final surface topography and XPS measurements to analyze the chemical composition of the samples after RIBE.

  5. Formation of iron nanoparticles and increase in iron reactivity in mineral dust during simulated cloud processing.

    Science.gov (United States)

    Shi, Zongbo; Krom, Michael D; Bonneville, Steeve; Baker, Alex R; Jickells, Timothy D; Benning, Liane G

    2009-09-01

    The formation of iron (Fe) nanoperticles and increase in Fe reactivity in mineral dust during simulated cloud processing was investigated using high-resolution microscopy and chemical extraction methods. Cloud processing of dust was experimentally simulated via an alternation of acidic (pH 2) and circumneutral conditions (pH 5-6) over periods of 24 h each on presieved (formation of Fe-rich nanoparticle aggregates, which were not found initially. Similar Fe-rich nanoparticles were also observed in wet-deposited Saharen dusts from the western Mediterranean but not in dry-deposited dust from the eastern Mediterranean. Sequential Fe extraction of the soil samples indicated an increase in the proportion of chemically reactive Fe extractable by an ascorbate solution after simulated cloud processing. In addition, the sequential extractions on the Mediterranean dust samples revealed a higher content of reactive Fe in the wet-deposited dust compared to that of the dry-deposited dust These results suggestthat large variations of pH commonly reported in aerosol and cloud waters can trigger neo-formation of nanosize Fe particles and an increase in Fe reactivity in the dust

  6. Nanoscale multilayered and porous carbide interphases prepared by pressure-pulsed reactive chemical vapor deposition for ceramic matrix composites

    International Nuclear Information System (INIS)

    Jacques, S.; Jouanny, I.; Ledain, O.; Maillé, L.; Weisbecker, P.

    2013-01-01

    In Ceramic Matrix Composites (CMCs) reinforced by continuous fibers, a good toughness is achieved by adding a thin film called “interphase” between the fiber and the brittle matrix, which acts as a mechanical fuse by deflecting the matrix cracks. Pyrocarbon (PyC), with or without carbide sub-layers, is typically the material of choice to fulfill this role. The aim of this work was to study PyC-free nanoscale multilayered carbide coatings as interphases for CMCs. Nanoscale multilayered (SiC–TiC) n interphases were deposited by pressure-Pulsed Chemical Vapor Deposition (P-CVD) on single filament Hi-Nicalon fibers and embedded in a SiC matrix sheath. The thicknesses of the carbide interphase sub-layers could be made as low as a few nanometers as evidenced by scanning and transmission electron microscopy. By using the P-ReactiveCVD method (P-RCVD), in which the TiC growth involves consumption of SiC, it was not only possible to obtain multilayered (SiC–TiC) n films but also TiC films with a porous multilayered microstructure as a result of the Kirkendall effect. The porosity in the TiC sequences was found to be enhanced when some PyC was added to SiC prior to total RCVD consumption. Because the porosity volume fraction was still not high enough, the role of mechanical fuse of the interphases could not be evidenced from the tensile curves, which remained fully linear even when chemical attack of the fiber surface was avoided.

  7. Nanoscale multilayered and porous carbide interphases prepared by pressure-pulsed reactive chemical vapor deposition for ceramic matrix composites

    Science.gov (United States)

    Jacques, S.; Jouanny, I.; Ledain, O.; Maillé, L.; Weisbecker, P.

    2013-06-01

    In Ceramic Matrix Composites (CMCs) reinforced by continuous fibers, a good toughness is achieved by adding a thin film called "interphase" between the fiber and the brittle matrix, which acts as a mechanical fuse by deflecting the matrix cracks. Pyrocarbon (PyC), with or without carbide sub-layers, is typically the material of choice to fulfill this role. The aim of this work was to study PyC-free nanoscale multilayered carbide coatings as interphases for CMCs. Nanoscale multilayered (SiC-TiC)n interphases were deposited by pressure-Pulsed Chemical Vapor Deposition (P-CVD) on single filament Hi-Nicalon fibers and embedded in a SiC matrix sheath. The thicknesses of the carbide interphase sub-layers could be made as low as a few nanometers as evidenced by scanning and transmission electron microscopy. By using the P-ReactiveCVD method (P-RCVD), in which the TiC growth involves consumption of SiC, it was not only possible to obtain multilayered (SiC-TiC)n films but also TiC films with a porous multilayered microstructure as a result of the Kirkendall effect. The porosity in the TiC sequences was found to be enhanced when some PyC was added to SiC prior to total RCVD consumption. Because the porosity volume fraction was still not high enough, the role of mechanical fuse of the interphases could not be evidenced from the tensile curves, which remained fully linear even when chemical attack of the fiber surface was avoided.

  8. Coupling between solute transport and chemical reactions models

    International Nuclear Information System (INIS)

    Samper, J.; Ajora, C.

    1993-01-01

    During subsurface transport, reactive solutes are subject to a variety of hydrodynamic and chemical processes. The major hydrodynamic processes include advection and convection, dispersion and diffusion. The key chemical processes are complexation including hydrolysis and acid-base reactions, dissolution-precipitation, reduction-oxidation, adsorption and ion exchange. The combined effects of all these processes on solute transport must satisfy the principle of conservation of mass. The statement of conservation of mass for N mobile species leads to N partial differential equations. Traditional solute transport models often incorporate the effects of hydrodynamic processes rigorously but oversimplify chemical interactions among aqueous species. Sophisticated chemical equilibrium models, on the other hand, incorporate a variety of chemical processes but generally assume no-flow systems. In the past decade, coupled models accounting for complex hydrological and chemical processes, with varying degrees of sophistication, have been developed. The existing models of reactive transport employ two basic sets of equations. The transport of solutes is described by a set of partial differential equations, and the chemical processes, under the assumption of equilibrium, are described by a set of nonlinear algebraic equations. An important consideration in any approach is the choice of primary dependent variables. Most existing models cannot account for the complete set of chemical processes, cannot be easily extended to include mixed chemical equilibria and kinetics, and cannot handle practical two and three dimensional problems. The difficulties arise mainly from improper selection of the primary variables in the transport equations. (Author) 38 refs

  9. Journal of Chemical Sciences | Indian Academy of Sciences

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences. ANAMIKA PAUL. Articles written in Journal of Chemical Sciences. Volume 128 Issue 7 July 2016 pp 1025-1032 Regular Article. Reactivity of [Cp*Mo(CO)₃Me] with chalcogenated borohydrides Li[BH₂E₃] and Li[BH₃EFc] (Cp* = (ŋ⁵-C₅Me₅); E = S, Se or Te; ...

  10. Advancements in Development of Chemical-Looping Combustion: A Review

    Directory of Open Access Journals (Sweden)

    He Fang

    2009-01-01

    Full Text Available Chemical-looping combustion (CLC is a novel combustion technology with inherent separation of greenhouse CO2. Extensive research has been performed on CLC in the last decade with respect to oxygen carrier development, reaction kinetics, reactor design, system efficiencies, and prototype testing. Transition metal oxides, such as Ni, Fe, Cu, and Mn oxides, were reported as reactive species in the oxygen carrier particles. Ni-based oxygen carriers exhibited the best reactivity and stability during multiredox cycles. The performance of the oxygen carriers can be improved by changing preparation method or by making mixedoxides. The CLC has been demonstrated successfully in continuously operated prototype reactors based on interconnected fluidized-bed system in the size range of 0.3–50 kW. High fuel conversion rates and almost 100%  CO2 capture efficiencies were obtained. The CLC system with two interconnected fluidized-bed reactors was considered the most suitable reactor design. Development of oxygen carriers with excellent reactivity and stability is still one of the challenges for CLC in the near future. Experiences of building and operating the large-scale CLC systems are needed before this technology is used commercially. Chemical-looping reforming (CLR and chemical-looping hydrogen (CLH are novel chemical-looping techniques to produce synthesis gas and hydrogen deserving more attention and research.

  11. Removal of reactive dyes from wastewater by shale

    Directory of Open Access Journals (Sweden)

    Jareeya Yimrattanabovorn

    2012-02-01

    Full Text Available Colored textile effluents represent severe environmental problems as they contain mixture of chemicals, auxiliariesand dyestuffs of different classes and chemical constitutions. Elimination of dyes in the textile wastewater by conventionalwastewater treatment methods is very difficult. At present, there is a growing interest in using inexpensive and potentialmaterials for the adsorption of reactive dyes. Shale has been reported to be a potential media to remove color from wastewaterbecause of its chemical characteristics. In this study, shale was used as an adsorbent. The chosen shale had particlesizes of : A (1.00 < A < 2.00 mm, B (0.50 < B < 1.00 mm, C (0.25 < C < 0.50 mm, D (0.18 < D < 0.25 mm and E (0.15 < E < 0.18mm. Remazol Deep Red RGB (Red, Remazol Brilliant Blue RN gran (Blue and Remazol Yellow 3RS 133% gran (Yellow wereused as adsorbates. Batch adsorption experiments were performed to investigate the effect of contact time, pH, temperatureand initial dye concentration. It was found that the equilibrium data were best described by the Langmuir isotherm model,with the maximum monolayer adsorption capacities of 0.0110-0.0322 mg/g for Red, 0.4479-1.1409 mg/g for Blue and 0.0133-0.0255 mg/g for Yellow, respectively. The maximum adsorption capacity of reactive dye by shale occurred at an initial pH of 2,initial concentration of 700 Pt-Co and temperature 45°C. Reactive dye adsorption capacities increased with an increase of theinitial dye concentration and temperature whereas with a decrease of pH. The fixed bed column experiments were appliedwith actual textile wastewater for estimation of life span. The results showed that COD and color removal efficiencies of shalefix bed column were 97% and 90%, respectively. Also the shale fixed bed columns were suitable for using with textile effluentfrom activated sludge system because of their COD and color removal efficiencies and life expectancy comparison using withdyebath wastewater and raw

  12. 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.

  13. The iodine reactivity; La reactivite de l'iode

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    2003-07-01

    The iodine is an important element because it has long life isotopes (such as iodine 129) and a great mobility in natural media. Iodine presents a complex chemistry because of its volatility and its strong redox reactivity. The S.E.C.R. works to better understand the reactivity of this element in different natural, industrial or biological environments. It plays a part in thermochemical sites as a possible way of hydrogen formation. This seminar gives some aspects relative to the chemical reactivity of iodine, since its thermochemistry in the I/S cycles to produce hydrogen to its reactivity in the natural medium and its potential radiological impact. This document includes 4 presentations transparencies dealing with: the {sup 129}I cycle rejected in the low radioactive gaseous and liquid effluents of the La Hague reprocessing plant (C. Frechou); a bibliographic review of iodine retention in soils (F. Bazer-Bachi); the hydrogen production and the iodine/sulfur thermochemical cycle (role of iodine in the process); and the direct characterization by electro-spray ionization mass spectroscopy of iodine fixation by fulvic acids (P. Reiller, B. Amekraz, C. Moulin, V. Moulin)

  14. Benchscale Assessment of the Efficacy of a Reactive Core Mat to Isolate PAH-spiked Aquatic Sediments.

    Science.gov (United States)

    Meric, Dogus; Barbuto, Sara; Sheahan, Thomas C; Shine, James P; Alshawabkeh, Akram N

    2014-01-01

    This paper describes the results of a benchscale testing program to assess the efficacy of a reactive core mat (RCM) for short term isolation and partial remediation of contaminated, subaqueous sediments. The 1.25 cm thick RCM (with a core reactive material such as organoclay with filtering layers on top and bottom) is placed on the sediment, and approximately 7.5 - 10 cm of overlying soil is placed on the RCM for stability and protection. A set of experiments were conducted to measure the sorption characteristics of the mat core (organoclay) and sediment used in the experiments, and to determine the fate of semi-volatile organic contaminants and non-reactive tracers through the sediment and reactive mat. The experimental study was conducted on naphthalene-spiked Neponset River (Milton, MA) sediment. The results show nonlinear sorption behavior for organoclay, with sorption capacity increasing with increasing naphthalene concentration. Neponset River sediment showed a notably high sorption capacity, likely due to the relatively high organic carbon fraction (14%). The fate and transport experiments demonstrated the short term efficiency of the reactive mat to capture the contamination that is associated with the post-capping period during which the highest consolidation-induced advective flux occurs, driving solid particles, pore fluid and soluble contaminants toward the reactive mat. The goal of the mat placement is to provide a physical filtering and chemically reactive layer to isolate contamination from the overlying water column. An important finding is that because of the high sorption capacity of the Neponset River sediment, the physical filtering capability of the mat is as critical as its chemical reactive capacity.

  15. Single and double carbon vacancies in pyrene as first models for graphene defects: A survey of the chemical reactivity toward hydrogen

    Science.gov (United States)

    Nieman, Reed; Das, Anita; Aquino, Adélia J. A.; Amorim, Rodrigo G.; Machado, Francisco B. C.; Lischka, Hans

    2017-01-01

    Graphene is regarded as one of the most promising materials for nanoelectronics applications. Defects play an important role in modulating its electronic properties and also enhance its chemical reactivity. In this work the reactivity of single vacancies (SV) and double vacancies (DV) in reaction with a hydrogen atom Hr is studied. Because of the complicated open shell electronic structures of these defects due to dangling bonds, multireference configuration interaction (MRCI) methods are being used in combination with a previously developed defect model based on pyrene. Comparison of the stability of products derived from Csbnd Hr bond formation with different carbon atoms of the different polyaromatic hydrocarbons is made. In the single vacancy case the most stable structure is the one where the incoming hydrogen is bound to the carbon atom carrying the dangling bond. However, stable Csbnd Hr bonded structures are also observed in the five-membered ring of the single vacancy. In the double vacancy, most stable bonding of the reactant Hr atom is found in the five-membered rings. In total, Csbnd Hr bonds, corresponding to local energy minimum structures, are formed with all carbon atoms in the different defect systems and the pyrene itself. Reaction profiles for the four lowest electronic states show in the case of a single vacancy a complex picture of curve crossings and avoided crossings which will give rise to a complex nonadiabatic reaction dynamics involving several electronic states.

  16. Atmospheric photochemical reactivity and ozone production at two sites in Hong Kong: Application of a Master Chemical Mechanism-photochemical box model

    Science.gov (United States)

    Ling, Z. H.; Guo, H.; Lam, S. H. M.; Saunders, S. M.; Wang, T.

    2014-09-01

    A photochemical box model incorporating the Master Chemical Mechanism (v3.2), constrained with a full suite of measurements, was developed to investigate the photochemical reactivity of volatile organic compounds at a semirural site (Mount Tai Mo Shan (TMS)) and an urban site (Tsuen Wan (TW)) in Hong Kong. The levels of ozone (O3) and its precursors, and the magnitudes of the reactivity of O3 precursors, revealed significant differences in the photochemistry at the two sites. Simulated peak hydroperoxyl radical (HO2) mixing ratios were similar at TW and TMS (p = 0.05), while the simulated hydroxyl radical (OH) mixing ratios were much higher at TW (p TMS, but at TW, both HCHO and O3 photolyses were found to be major contributors. By contrast, radical-radical reactions governed HOx radical losses at TMS, while at TW, the OH + NO2 reaction was found to dominate in the morning and the radical-radical reactions at noon. Overall, the conversion of NO to NO2 by HO2 dictated the O3 production at the two sites, while O3 destruction was dominated by the OH + NO2 reaction at TW, and at TMS, O3 photolysis and the O3 + HO2 reaction were the major mechanisms. The longer OH chain length at TMS indicated that more O3 was produced for each radical that was generated at this site.

  17. Molecular structure, chemical reactivity, nonlinear optical activity and vibrational spectroscopic studies on 6-(4-n-heptyloxybenzyoloxy)-2-hydroxybenzylidene)amino)-2H-chromen-2-one: A combined density functional theory and experimental approach

    Science.gov (United States)

    Pegu, David; Deb, Jyotirmoy; Saha, Sandip Kumar; Paul, Manoj Kumar; Sarkar, Utpal

    2018-05-01

    In this work, we have synthesized new coumarin Schiff base molecule, viz., 6-(4-n-heptyloxybenzyoloxy)-2-hydroxybenzylidene)amino)-2H-chromen-2-one and characterized its structural, electronic and spectroscopic properties experimentally and theoretically. The theoretical analysis of UV-visible absorption spectra reflects a red shift in the absorption maximum in comparison to the experimental results. Most of the vibrational assignments of infrared and Raman spectra predicted using density functional theory approach match well with the experimental findings. Further, the chemical reactivity analysis confirms that solvent highly affects the reactivity of the studied compound. The large hyperpolarizability value of the compound concludes that the system exhibits significant nonlinear optical features and thus, points out their possibility in designing material with high nonlinear activity.

  18. Reactivation and reuse of TiO2-SnS2 composite catalyst for solar-driven water treatment.

    Science.gov (United States)

    Kovacic, Marin; Kopcic, Nina; Kusic, Hrvoje; Stangar, Urska Lavrencic; Dionysiou, Dionysios D; Bozic, Ana Loncaric

    2018-01-01

    One of the most important features of photocatalytic materials intended to be used for water treatment is their long-term stability. The study is focused on the application of thermal and chemical treatments for the reactivation of TiO 2 -SnS 2 composite photocatalyst, prepared by hydrothermal synthesis and immobilized on the glass support using titania/silica binder. Such a catalytic system was applied in solar-driven treatment, solar/TiO 2 -SnS 2 /H 2 O 2 , for the purification of water contaminated with diclofenac (DCF). The effectiveness of studied reactivation methods for retaining TiO 2 -SnS 2 activity in consecutive cycles was evaluated on basis of DCF removal and conversion, and TOC removal and mineralization of organic content. Besides these water quality parameters, biodegradability changes in DCF aqueous solution treated by solar/TiO 2 -SnS 2 /H 2 O 2 process using simply reused (air-dried) and thermally and chemically reactivated composite photocatalyst through six consecutive cycles were monitored. It was established that both thermal and chemical reactivation retain TiO 2 -SnS 2 activity in the second cycle of its reuse. However, both treatments caused the alteration in the TiO 2 -SnS 2 morphology due to the partial transformation of visible-active SnS 2 into non-active SnO 2 . Such alteration, repeated through consecutive reactivation and reuse, was reflected through gradual activity loss of TiO 2 -SnS 2 composite in applied solar-driven water treatment.

  19. T cell reactivity with allergoids: influence of the type of APC.

    Science.gov (United States)

    Kahlert, H; Grage-Griebenow, E; Stüwe, H T; Cromwell, O; Fiebig, H

    2000-08-15

    The use of allergoids for allergen-specific immunotherapy has been established for many years. The characteristic features of these chemically modified allergens are their strongly reduced IgE binding activity compared with the native form and the retained immunogenicity. T cell reactivity of chemically modified allergens is documented in animals, but in humans indirect evidence of reactivity has been concluded from the induction of allergen-specific IgG during immunotherapy. Direct evidence of T cell reactivity was obtained recently using isolated human T cells. To obtain further insight into the mechanism of action of allergoids, we compared the Ag-presenting capacity of different APC types, including DC and macrophages, generated from CD14+ precursor cells from the blood of grass pollen allergic subjects, autologous PBMC, and B cells. These APC were used in experiments together with Phl p 5-specific T cell clones under stimulation with grass pollen allergen extract, rPhl p 5b, and the respective allergoids. Using DC and macrophages, allergoids exhibited a pronounced and reproducible T cell-stimulating capacity. Responses were superior to those with PBMC, and isolated B cells failed to present allergoids. Considerable IL-12 production was observed only when using the DC for Ag presentation of both allergens and allergoids. The amount of IL-10 in supernatants was dependent on the phenotype of the respective T cell clone. High IL-10 production was associated with suppressed IL-12 production from the DC in most cases. In conclusion, the reactivity of Th cells with allergoids is dependent on the type of the APC.

  20. Role of substituents on the reactivity and electron density profile of ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 125; Issue 5. Role of substituents on the reactivity and electron density profile of diimine ligands: A density functional theory based study. Bhakti S Kulkarni Deepti Mishra Sourav Pal. Volume 125 Issue 5 September 2013 pp 1247-1258 ...

  1. Control of Reactive Species Generated by Low-frequency Biased Nanosecond Pulse Discharge in Atmospheric Pressure Plasma Effluent

    Science.gov (United States)

    Takashima, Keisuke; Kaneko, Toshiro

    2016-09-01

    The control of hydroxyl radical and the other gas phase species generation in the ejected gas through air plasma (air plasma effluent) has been experimentally studied, which is a key to extend the range of plasma treatment. Nanosecond pulse discharge is known to produce high reduced electric field (E/N) discharge that leads to efficient generation of the reactive species than conventional low frequency discharge, while the charge-voltage cycle in the low frequency discharge is known to be well-controlled. In this study, the nanosecond pulse discharge biased with AC low frequency high voltage is used to take advantages of these discharges, which allows us to modulate the reactive species composition in the air plasma effluent. The utilization of the gas-liquid interface and the liquid phase chemical reactions between the modulated long-lived reactive species delivered from the air plasma effluent could realize efficient liquid phase chemical reactions leading to short-lived reactive species production far from the air plasma, which is crucial for some plasma agricultural applications.

  2. Structural and reactivity models for copper oxygenases: cooperative effects and novel reactivities.

    Science.gov (United States)

    Serrano-Plana, Joan; Garcia-Bosch, Isaac; Company, Anna; Costas, Miquel

    2015-08-18

    Dioxygen is widely used in nature as oxidant. Nature itself has served as inspiration to use O2 in chemical synthesis. However, the use of dioxygen as an oxidant is not straightforward. Its triplet ground-state electronic structure makes it unreactive toward most organic substrates. In natural systems, metalloenzymes activate O2 by reducing it to more reactive peroxide (O2(2-)) or superoxide (O2(-)) forms. Over the years, the development of model systems containing transition metals has become a convenient tool for unravelling O2-activation mechanistic aspects and reproducing the oxidative activity of enzymes. Several copper-based systems have been developed within this area. Tyrosinase is a copper-based O2-activating enzyme, whose structure and reactivity have been widely studied, and that serves as a paradigm for O2 activation at a dimetal site. It contains a dicopper center in its active site, and it catalyzes the regioselective ortho-hydroxylation of phenols to catechols and further oxidation to quinones. This represents an important step in melanin biosynthesis and it is mediated by a dicopper(II) side-on peroxo intermediate species. In the present accounts, our research in the field of copper models for oxygen activation is collected. We have developed m-xylyl linked dicopper systems that mimick structural and reactivity aspects of tyrosinase. Synergistic cooperation of the two copper(I) centers results in O2 binding and formation of bis(μ-oxo)dicopper(III) cores. These in turn bind and ortho-hydroxylate phenolates via an electrophilic attack of the oxo ligand over the arene. Interestingly the bis(μ-oxo)dicopper(III) cores can also engage in ortho-hydroxylation-defluorination of deprotonated 2-fluorophenols, substrates that are well-known enzyme inhibitors. Analysis of Cu2O2 species with different binding modes show that only the bis(μ-oxo)dicopper(III) cores can mediate the reaction. Finally, the use of unsymmetric systems for oxygen activation is a field

  3. Clinical and immunological investigations of respiratory disease in workers using reactive dyes.

    Science.gov (United States)

    Docker, A; Wattie, J M; Topping, M D; Luczynska, C M; Newman Taylor, A J; Pickering, C A; Thomas, P; Gompertz, D

    1987-01-01

    A questionnaire survey of over 400 workers handling reactive dyes showed that over 15% had work related respiratory or nasal symptoms. Forty nine employees with symptoms were referred to chest clinics for detailed assessment. It was considered that in 19 the symptoms could be attributed to an irritant response to a variety of chemicals, including hydrochloric acid vapour, sulphur dioxide, and reactive dyes. Symptoms in 24 were attributed to an allergic reaction to a specific agent; in most (21) to one or more reactive dyes. Two patterns of allergic lower respiratory symptoms were identified; an immediate response of short duration and a longer lasting response, usually of several hours, sometimes accompanied by nocturnal asthma. A radioallergosorbent test (RAST) screen containing the most commonly used reactive dyes was used to detect specific IgE. Allergic symptoms to reactive dyes were strongly associated with specific IgE (17/21 employees) and atopy (18/21). Irritant symptoms were also associated with atopy (13/19) but only weakly associated with specific IgE (7/19). PMID:3651352

  4. Centrally Acting Oximes in Reactivation of Tabun-Phosphoramidated AChE

    Science.gov (United States)

    Kovarik, Zrinka; Maček, Nikolina; Sit, Rakesh K.; Radić, Zoran; Fokin, Valery V.; Sharpless, K. Barry; Taylor, Palmer

    2012-01-01

    Organophosphates (OP) inhibit acetylcholinesterase (AChE, E.C.3.1.1.7), both in peripheral tissues and central nervous system (CNS), causing adverse and sometimes fatal effects due to the accumulation of neurotransmitter acetylcholine (ACh). The currently used therapy, focusing on the reactivation of inhibited AChE, is limited to peripheral tissues because commonly used quaternary pyridinium oxime reactivators do not cross the blood brain barrier (BBB) at therapeutically relevant levels. A directed library of thirty uncharged oximes that contain tertiary amine or imidazole protonable functional groups that should cross the BBB as unionized species was tested as tabun-hAChE conjugate reactivators along with three reference oximes: DAM (diacetylmonoxime), MINA (monoisonitrosoacetone), and 2-PAM. The oxime RS150D [N-((1-(3-(2-((hydroxyimino)methyl)-1H-imidazol-1-yl)propyl)-1H-1,2,3-triazol-4-yl)methyl)benzamide] was highlighted as the most promising reactivator of the tabun-hAChE conjugate. We also observed that oximes RS194B [N-(2-(azepan-1-yl)ethyl)-2-(hydroxyimino)acetamide] and RS41A [2-(hydroxyimino)-N-(2-(pyrrolidin-1-yl)ethyl)acetamide], which emerged as lead uncharged reactivators of phosphylated hAChE with other OPs (sarin, cyclosarin and VX), exhibited only moderate reactivation potency for tabun inhibited hAChE. This implies that geometry of oxime access to the phosphorus atom conjugated to the active serine is an important criterion for efficient reactivation, along with the chemical nature of the conjugated moiety: phosphorate, phosphonate, or phosphoramidate. Moreover, modification of the active center through mutagenesis enhances the rates of reactivation. The phosphoramidated-hAChE choline-binding site mutant Y337A showed three-times enhanced reactivation capacity with non-triazole imidazole containing aldoximes (RS113B, RS113A and RS115A) and acetamide derivative (RS194B) than with 2PAM. PMID:22960624

  5. Modification of the finite element heat and mass transfer code (FEHMN) to model multicomponent reactive transport

    International Nuclear Information System (INIS)

    Viswanathan, H.S.

    1995-01-01

    The finite element code FEHMN is a three-dimensional finite element heat and mass transport simulator that can handle complex stratigraphy and nonlinear processes such as vadose zone flow, heat flow and solute transport. Scientists at LANL have been developed hydrologic flow and transport models of the Yucca Mountain site using FEHMN. Previous FEHMN simulations have used an equivalent K d model to model solute transport. In this thesis, FEHMN is modified making it possible to simulate the transport of a species with a rigorous chemical model. Including the rigorous chemical equations into FEHMN simulations should provide for more representative transport models for highly reactive chemical species. A fully kinetic formulation is chosen for the FEHMN reactive transport model. Several methods are available to computationally implement a fully kinetic formulation. Different numerical algorithms are investigated in order to optimize computational efficiency and memory requirements of the reactive transport model. The best algorithm of those investigated is then incorporated into FEHMN. The algorithm chosen requires for the user to place strongly coupled species into groups which are then solved for simultaneously using FEHMN. The complete reactive transport model is verified over a wide variety of problems and is shown to be working properly. The simulations demonstrate that gas flow and carbonate chemistry can significantly affect 14 C transport at Yucca Mountain. The simulations also provide that the new capabilities of FEHMN can be used to refine and buttress already existing Yucca Mountain radionuclide transport studies

  6. Numerical investigation on the effect of reactivity gradient in an RCCI engine fueled with gasoline and diesel

    International Nuclear Information System (INIS)

    Li, J.; Yang, W.M.; An, H.; Zhou, D.Z.; Yu, W.B.; Wang, J.X.; Li, L.

    2015-01-01

    Highlights: • A chemical reaction mechanism is newly developed for dual fuel combustion. • The developed chemical kinetics is coupled with KIVA4 to model the combustion. • The role of reactivity gradient in RCCI combustion is investigated. • The RCCI (dual fuel mode) combustion is compared with blend fuel mode. - Abstract: The reactivity controlled compression ignition (RCCI), which belongs to dual fuel mode (DFM) combustion has been considered as a promising way to achieve high fuel conversion efficiency and low emissions. By this strategy, a fuel reactivity gradient is formed in the combustion chamber which offers the probability of controlling combustion phasing. In this study, the role of fuel reactivity gradient was examined numerically by comparing a DFM (i.e., RCCI) combustion with other hypothetical cases under one specific load condition. Firstly, a chemical reaction mechanism was developed aiming at a modelling study on dual fuel and blend fuel combustion in internal combustion (IC) engines fueled by gasoline/diesel and gasoline/biodiesel. Ignition delays were validated for 100% diesel, 100% gasoline and 100% biodiesel under 102 conditions in total. Subsequently, the validated reaction mechanism which consists of 107 species and 425 reactions was implemented in coupled KIVA4-CHEMKIN code. Three dimensional validations were further conducted under 3 conditions including pure diesel combustion, and gasoline/diesel DFM combustion with both single and double injection strategies in the engine. To investigate the fuel reactivity gradient, the gasoline/diesel DFM combustion with single injection was compared with other three hypothetical cases, one of which was DFM without fuel reactivity gradient, two were the blend fuel mode but with different start of injection (SOI) timings. The results showed that the fuel reactivity gradient could retard the ignition timing, reduce heat release rate, and ease peak pressure rise rate. In addition, low levels of NO

  7. Internal Domains of Natural Porous Media Revealed: Critical Locations for Transport, Storage, and Chemical Reaction

    Energy Technology Data Exchange (ETDEWEB)

    Zachara, John M.; Brantley, Susan L.; Chorover, Jon D.; Ewing, Robert P.; Kerisit, Sebastien N.; Liu, Chongxuan; Perfect, E.; Rother, Gernot; Stack, Andrew G.

    2016-03-16

    Internal pore domains exist within rocks, lithic fragments, subsurface sediments and soil aggregates. These domains, which we term internal domains in porous media (IDPM), contain a significant fraction of their porosity as nanopores, dominate the reactive surface area of diverse porous media types, and are important locations for chemical reactivity and hydrocarbon storage. Traditionally difficult to interrogate, advances in instrumentation and imaging methods are providing new insights on the physical structures and chemical attributes of IDPM. In this review we: discuss analytical methods to characterize IDPM, evaluate what has been learned about their size distributions, connectivity, and extended structures; determine whether they exhibit unique chemical reactivity; and assess potential for their inclusion in reactive transport models. Three key findings are noteworthy. 1) A combination of methods now allows complete characterization of the porosity spectrum of natural materials and its connectivity; while imaging microscopies are providing three dimensional representations of the interconnected pore network. 2) Chemical reactivity in pores <10 nm is expected to be different from micro and macropores, yet research performed to date is inconclusive on the nature, direction, and magnitude of effect. 3) Existing continuum reactive transport models treat IDPM as a sub-grid feature with average, empirical, scale-dependent parameters; and are not formulated to include detailed information on pore networks. Overall we find that IDPM are key features controlling hydrocarbon release from shales in hydrofracking systems, organic matter stabilization and recalcitrance in soil, weathering and soil formation, and long term inorganic and organic contaminant behavior in the vadose zone and groundwater. We conclude with an assessment of impactful research opportunities to advance understanding of IDPM, and to incorporate their important effects in reactive transport models

  8. 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.

  9. Diazo Compounds: Versatile Tools for Chemical Biology

    OpenAIRE

    Mix, Kalie A.; Aronoff, Matthew R.; Raines, Ronald T.

    2016-01-01

    Diazo groups have broad and tunable reactivity. That and other attributes endow diazo compounds with the potential to be valuable reagents for chemical biologists. The presence of diazo groups in natural products underscores their metabolic stability and anticipates their utility in a biological context. The chemoselectivity of diazo groups, even in the presence of azido groups, presents many opportunities. Already, diazo compounds have served as chemical probes and elicited novel modificatio...

  10. Thiol-ene thermosets exploiting surface reactivity for layer-by-layer structures and control of penetration depth for selective surface reactivity

    DEFF Research Database (Denmark)

    Daugaard, Anders Egede; Westh, Andreas; Pereira Rosinha Grundtvig, Ines

    Thiol-ene thermosets have been shown to be an efficient platform for preparation of functional polymer surfaces. Especially the effectiveness and versatility of the system has enabled a large variety of network properties to be obtained in a simple and straight-forward way. Due to its selectivity......, various thiols and allyl or other vinyl reactants can be used to obtain either soft and flexible1 or more rigid functional thermosets 2. The methodology permits use of etiher thermal or photochemical conditions both for matrix preparation as well as for surface functionalization. Due to excess reactive...... groups in thµe surface of thiol-ene thermosets, it is possible to prepare surface functional thermosets or to exploit the reactive groups for modular construction and subsequent chemical bonding. Here a different approach preparing monolithic layer-by-layer structures with controlled mechanical...

  11. Reactive ion assisted deposition of aluminum oxynitride thin films

    International Nuclear Information System (INIS)

    Hwangbo, C.K.; Lingg, L.J.; Lehan, J.P.; Macleod, H.A.; Suits, F.

    1989-01-01

    Optical properties, stoichiometry, chemical bonding states, and crystal structure of aluminum oxynitride (AlO/sub x/N/sub y/) thin films prepared by reactive ion assisted deposition were investigated. The results show that by controlling the amount of reactive gases the refractive index of aluminum oxynitride films at 550 nm is able to be varied from 1.65 to 1.83 with a very small extinction coefficient. Variations of optical constants and chemical bonding states of aluminum oxynitride films are related to the stoichiometry. From an x-ray photoelectron spectroscopy analysis it is observed that our aluminum oxynitride film is not simply a mixture of aluminum oxide and aluminum nitride but a continuously variable compound. The aluminum oxynitride films are amorphous from an x-ray diffraction analysis. A rugate filter using a step index profile of aluminum oxynitride films was fabricated by nitrogen ion beam bombardment of a growing Al film with backfill oxygen pressure as the sole variation. This filter shows a high resistivity to atmospheric moisture adsorption, suggesting that the packing density of aluminum oxynitride films is close to unity and the energetic ion bombardment densifies the film as well as forming the compound

  12. Reactive Kripke semantics

    CERN Document Server

    Gabbay, Dov M

    2013-01-01

    This text offers an extension to the traditional Kripke semantics for non-classical logics by adding the notion of reactivity. Reactive Kripke models change their accessibility relation as we progress in the evaluation process of formulas in the model. This feature makes the reactive Kripke semantics strictly stronger and more applicable than the traditional one. Here we investigate the properties and axiomatisations of this new and most effective semantics, and we offer a wide landscape of applications of the idea of reactivity. Applied topics include reactive automata, reactive grammars, rea

  13. Modification of the finite element heat and mass transfer code (FEHM) to model multicomponent reactive transport

    International Nuclear Information System (INIS)

    Viswanathan, H.S.

    1996-08-01

    The finite element code FEHMN, developed by scientists at Los Alamos National Laboratory (LANL), is a three-dimensional finite element heat and mass transport simulator that can handle complex stratigraphy and nonlinear processes such as vadose zone flow, heat flow and solute transport. Scientists at LANL have been developing hydrologic flow and transport models of the Yucca Mountain site using FEHMN. Previous FEHMN simulations have used an equivalent Kd model to model solute transport. In this thesis, FEHMN is modified making it possible to simulate the transport of a species with a rigorous chemical model. Including the rigorous chemical equations into FEHMN simulations should provide for more representative transport models for highly reactive chemical species. A fully kinetic formulation is chosen for the FEHMN reactive transport model. Several methods are available to computationally implement a fully kinetic formulation. Different numerical algorithms are investigated in order to optimize computational efficiency and memory requirements of the reactive transport model. The best algorithm of those investigated is then incorporated into FEHMN. The algorithm chosen requires for the user to place strongly coupled species into groups which are then solved for simultaneously using FEHMN. The complete reactive transport model is verified over a wide variety of problems and is shown to be working properly. The new chemical capabilities of FEHMN are illustrated by using Los Alamos National Laboratory's site scale model of Yucca Mountain to model two-dimensional, vadose zone 14 C transport. The simulations demonstrate that gas flow and carbonate chemistry can significantly affect 14 C transport at Yucca Mountain. The simulations also prove that the new capabilities of FEHMN can be used to refine and buttress already existing Yucca Mountain radionuclide transport studies

  14. Microstructure, chemical states, and mechanical properties of V–C–Co coatings prepared by non-reactive magnetron sputtering

    International Nuclear Information System (INIS)

    Zhang, Xiaojuan; Wang, Bo; Zhan, Zhaolin; Huang, Feng

    2013-01-01

    V–C–Co coatings have been prepared by non-reactive magnetron co-sputtering from VC and Co targets. The microstructure, chemical states, and mechanical properties are examined as a function of Co content in the coatings. The coatings are dense, with columnar growth structures. High resolution transmission electron microscopy (HRTEM) studies identify a nanocomposite microstructure for the 12.4 at.% Co coating, in which ligament-like Co-rich regions partially separate the nanocrystalline VC grains. X-ray photoelectron spectroscopy studies reveal a noticeable charge transfer from Co 2p states to C 1s states. This charge transfer, in addition to the ligament-like Co-rich regions as revealed by HRTEM, points to the formation of a strong Co/VC interface. The nanoindentation hardness of the coatings drops steadily with the Co content, from 29 GPa for pure VC to ∼ 21 GPa for the 12.4 at.% Co coating. Meanwhile, the plasticity characteristic increased from 0.42 to 0.53. - Highlights: • Nanocomposite V–C–Co coatings with strong Co/VC interfaces were formed. • Found nanocrystalline VC grains separated by ∼ 1 nm thin Co-rich ligaments. • A noticeable amount of C-Co bonds between VC and Co is identified. • V–C–Co coatings exhibited a higher plasticity characteristic than VC

  15. Microstructure, chemical states, and mechanical properties of V–C–Co coatings prepared by non-reactive magnetron sputtering

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Xiaojuan [Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo, Zhejiang 315201 (China); School of Materials Science and Engineering, Kunming University of Science and Technology, Kunming, Yunnan 650000 (China); Wang, Bo [Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo, Zhejiang 315201 (China); Zhan, Zhaolin [School of Materials Science and Engineering, Kunming University of Science and Technology, Kunming, Yunnan 650000 (China); Huang, Feng, E-mail: huangfeng@nimte.ac.cn [Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo, Zhejiang 315201 (China)

    2013-07-01

    V–C–Co coatings have been prepared by non-reactive magnetron co-sputtering from VC and Co targets. The microstructure, chemical states, and mechanical properties are examined as a function of Co content in the coatings. The coatings are dense, with columnar growth structures. High resolution transmission electron microscopy (HRTEM) studies identify a nanocomposite microstructure for the 12.4 at.% Co coating, in which ligament-like Co-rich regions partially separate the nanocrystalline VC grains. X-ray photoelectron spectroscopy studies reveal a noticeable charge transfer from Co 2p states to C 1s states. This charge transfer, in addition to the ligament-like Co-rich regions as revealed by HRTEM, points to the formation of a strong Co/VC interface. The nanoindentation hardness of the coatings drops steadily with the Co content, from 29 GPa for pure VC to ∼ 21 GPa for the 12.4 at.% Co coating. Meanwhile, the plasticity characteristic increased from 0.42 to 0.53. - Highlights: • Nanocomposite V–C–Co coatings with strong Co/VC interfaces were formed. • Found nanocrystalline VC grains separated by ∼ 1 nm thin Co-rich ligaments. • A noticeable amount of C-Co bonds between VC and Co is identified. • V–C–Co coatings exhibited a higher plasticity characteristic than VC.

  16. Chemical reactivities of the superconducting oxides, YBa2Cu3Oy and BiSrCaCu2Oy

    International Nuclear Information System (INIS)

    Toyama, Hisashi; Mizuno, Noritaka; Misono, Makoto

    1989-01-01

    The chemical reactivities of YBa 2 Cu 3 O y and BiSrCaCu 2 O y with various gases have been studied. It was found that large quantities of NO, CO, and NO 2 were rapidly absorbed (or intercalated) in the bulk of YBa 2 Cu 3 O y (T c : 90 K) at 573 K. The amount absorbed was in the order NO ∼ CO ∼ NO 2 > O 2 ∼ CO 2 > N 2 O ∼ 0. The amount for NO was more than two times the amount of YBa 2 Cu 3 O y in molar ratio and elongation by about 0.2 angstrom along c-axis was observed. NO absorbed was almost completely recovered as NO by the evacuation at 773 K. This absorption-desorption cycle proceeded reversively. The electronic resistivity at 573 K of YBa 2 Cu 3 O y increased upon the NO absorption and was restored by the evacuation at 773 K. CO was also absorbed rapidly accompanied by evolution of CO 2 . BiSrCaCu 2 O y did not absorb either NO or CO

  17. Use of Reactive Distillation for Biodiesel Production: A Literature Survey

    Directory of Open Access Journals (Sweden)

    Muhammad Dani Supardan

    2006-06-01

    Full Text Available Biodiesel has been shown to be the best substitute for fossil-based fuels to its environmental advantages and renewable resource availability. There is a great demand for the commercialization of biodiesel production, which in turn calls for a technically and economically reactor technology. The production of biodiesel in existing batch and continuous-flow processes requires excess alcohol, typically 100%, over the stoichiometric molar requirement in order to drive the chemical reaction to completion. In this study, a novel reactor system using a reactive distillation (RD technique was discussed for biodiesel production. RD is a chemical unit operation in which chemical reactions and separations occur simultaneously in one unit. It is an effective alternative to the classical combination of reactor and separation units especially when involving reversible or consecutive chemical reactions such as transesterication process in biodiesel production.

  18. Chemical Characterization and Reactivity Testing of Fuel-Oxidizer Reaction Product (Test Report)

    Science.gov (United States)

    1996-01-01

    The product of incomplete reaction of monomethylhydrazine (MMH) and nitrogen tetroxide (NTO) propellants, or fuel-oxidizer reaction product (FORP), has been hypothesized as a contributory cause of an anomaly which occurred in the chamber pressure (PC) transducer tube on the Reaction Control Subsystem (RCS) aft thruster 467 on flight STS-51. A small hole was found in the titanium-alloy PC tube at the first bend below the pressure transducer. It was surmised that the hole may have been caused by heat and pressure resulting from ignition of FORP. The NASA Johnson Space Center (JSC) White Sands Test Facility (WSTF) was requested to define the chemical characteristics of FORP, characterize its reactivity, and simulate the events in a controlled environment which may have lead to the Pc-tube failure. Samples of FORP were obtained from the gas-phase reaction of MMH with NTO under laboratory conditions, the pulsed firings of RCS thrusters with modified PC tubes using varied oxidizer or fuel lead times, and the nominal RCS thruster firings at WSTF and Kaiser-Marquardt. Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), accelerating rate calorimetry (ARC), ion chromatography (IC), inductively coupled plasma (ICP) spectrometry, thermogravimetric analysis (TGA) coupled to FTIR (TGA/FTIR), and mechanical impact testing were used to qualitatively and quantitatively characterize the chemical, thermal, and ignition properties of FORP. These studies showed that the composition of FORP is variable but falls within a limited range of compositions that depends on the fuel loxidizer ratio at the time of formation, composition of the post-formation atmosphere (reducing or oxidizing), and reaction or postreaction temperature. A typical composition contains methylhydrazinium nitrate (MMHN), ammonium nitrate (AN), methylammonium nitrate (MAN), and trace amounts of hydrazinium nitrate and 1,1-dimethylhydrazinium nitrate. The thermal decomposition

  19. Method for producing chemical energy

    Science.gov (United States)

    Jorgensen, Betty S.; Danen, Wayne C.

    2004-09-21

    Fluoroalkylsilane-coated metal particles having a central metal core, a buffer layer surrounding the core, and a fluoroalkylsilane layer attached to the buffer layer are prepared by combining a chemically reactive fluoroalkylsilane compound with an oxide coated metal particle having a hydroxylated surface. The resulting fluoroalkylsilane layer that coats the particles provides them with excellent resistance to aging. The particles can be blended with oxidant particles to form energetic powder that releases chemical energy when the buffer layer is physically disrupted so that the reductant metal core can react with the oxidant.

  20. Covalent functionalization of graphene with reactive intermediates.

    Science.gov (United States)

    Park, Jaehyeung; Yan, Mingdi

    2013-01-15

    Graphene, a material made exclusively of sp(2) carbon atoms with its π electrons delocalized over the entire 2D network, is somewhat chemically inert. Covalent functionalization can enhance graphene's properties including opening its band gap, tuning conductivity, and improving solubility and stability. Covalent functionalization of pristine graphene typically requires reactive species that can form covalent adducts with the sp(2) carbon structures in graphene. In this Account, we describe graphene functionalization reactions using reactive intermediates of radicals, nitrenes, carbenes, and arynes. These reactive species covalently modify graphene through free radical addition, CH insertion, or cycloaddition reactions. Free radical additions are among the most common reaction, and these radicals can be generated from diazonium salts and benzoyl peroxide. Electron transfer from graphene to aryl diazonium ion or photoactivation of benzoyl peroxide yields aryl radicals that subsequently add to graphene to form covalent adducts. Nitrenes, electron-deficient species generated by thermal or photochemical activation of organic azides, can functionalize graphene very efficiently. Because perfluorophenyl nitrenes show enhanced bimolecular reactions compared with alkyl or phenyl nitrenes, perfluorophenyl azides are especially effective. Carbenes are used less frequently than nitrenes, but they undergo CH insertion and C═C cycloaddition reactions with graphene. In addition, arynes can serve as a dienophile in a Diels-Alder type reaction with graphene. Further study is needed to understand and exploit the chemistry of graphene. The generation of highly reactive intermediates in these reactions leads to side products that complicate the product composition and analysis. Fundamental questions remain about the reactivity and regioselectivity of graphene. The differences in the basal plane and the undercoordinated edges of graphene and the zigzag versus arm-chair configurations

  1. Target surface condition during reactive glow discharge sputtering of copper

    International Nuclear Information System (INIS)

    Depla, D; Haemers, J; Gryse, R De

    2002-01-01

    During reactive glow discharge sputtering of copper in an argon/nitrogen plasma, we noticed an abrupt change of the target voltage and the deposition rate when the nitrogen concentration in the plasma exceeds a critical value. To explain this behaviour, the target surface after reactive glow discharge sputtering was examined by x-ray photoelectron spectroscopy (XPS). An experimental arrangement was constructed that allows direct transfer of the glow discharge cathode to the XPS analysis chamber without air exposure. These XPS measurements revealed that several different chemical states of nitrogen are present in the layer that forms on the target surface. The relative concentration of these different states changes when the critical nitrogen concentration in the plasma is exceeded

  2. Chemical Continuous Time Random Walks

    Science.gov (United States)

    Aquino, T.; Dentz, M.

    2017-12-01

    Traditional methods for modeling solute transport through heterogeneous media employ Eulerian schemes to solve for solute concentration. More recently, Lagrangian methods have removed the need for spatial discretization through the use of Monte Carlo implementations of Langevin equations for solute particle motions. While there have been recent advances in modeling chemically reactive transport with recourse to Lagrangian methods, these remain less developed than their Eulerian counterparts, and many open problems such as efficient convergence and reconstruction of the concentration field remain. We explore a different avenue and consider the question: In heterogeneous chemically reactive systems, is it possible to describe the evolution of macroscopic reactant concentrations without explicitly resolving the spatial transport? Traditional Kinetic Monte Carlo methods, such as the Gillespie algorithm, model chemical reactions as random walks in particle number space, without the introduction of spatial coordinates. The inter-reaction times are exponentially distributed under the assumption that the system is well mixed. In real systems, transport limitations lead to incomplete mixing and decreased reaction efficiency. We introduce an arbitrary inter-reaction time distribution, which may account for the impact of incomplete mixing. This process defines an inhomogeneous continuous time random walk in particle number space, from which we derive a generalized chemical Master equation and formulate a generalized Gillespie algorithm. We then determine the modified chemical rate laws for different inter-reaction time distributions. We trace Michaelis-Menten-type kinetics back to finite-mean delay times, and predict time-nonlocal macroscopic reaction kinetics as a consequence of broadly distributed delays. Non-Markovian kinetics exhibit weak ergodicity breaking and show key features of reactions under local non-equilibrium.

  3. Ethyl Acetate Synthesis by Coupling of Fixed-bed Reactor and Reactive Distillation Column—Process Integration Aspects

    Czech Academy of Sciences Publication Activity Database

    Smejkal, Q.; Kolena, J.; Hanika, Jiří

    2009-01-01

    Roč. 154, 1-3 (2009), s. 236-240 ISSN 1385-8947. [International Conference on Chemical Reactors - CHEMREACTOR -18 /18./. Malta, 23.09.2008-03.10.2008] Institutional research plan: CEZ:AV0Z40720504 Keywords : ethyl acetate * esterification * reactive distillation Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 2.816, year: 2009

  4. Effects of methyl group on aromatic hydrocarbons on the nanostructures and oxidative reactivity of combustion-generated soot

    KAUST Repository

    Guerrero Peñ a, Gerardo D.J.; Alrefaai, Mhd Maher; Yang, Seung Yeon; Raj, Abhijeet; Brito, Joaquin L.; Stephen, Samuel; Anjana, Tharalekshmy; Pillai, Vinu; Al Shoaibi, Ahmed; Chung, Suk-Ho

    2016-01-01

    The substituted and unsubstituted aromatic hydrocarbons, present in transportation fuels such as gasoline and diesel, are thought to be responsible for most of the soot particles produced during their combustion. However, the effects of the substituted alkyl groups on the aromatic hydrocarbons on their sooting tendencies, and on the physical and chemical properties of soot produced from them are not well understood. In this work, the effect of the presence of methyl groups on aromatic hydrocarbons on their sooting propensity, and on the oxidative reactivity, morphology, and chemical composition of soot generated from them in diffusion flames is studied using benzene, toluene, and m-xylene as fuels. Several experimental techniques including high resolution transmission electron microscopy and X-ray diffraction are used to identify the morphological changes in soot, whereas the elemental and thermo-gravimetric analyses, electron energy loss spectroscopy, and Fourier transform infrared spectroscopy are used to study the changes in its chemical properties and reactivity. The activation energies for soot oxidation are calculated at different conversion levels, and a trend in the reactivity of soots from benzene, toluene and m-xylene is reported. It is observed that the sizes of primary particles and graphene-like sheets, and the concentrations of aliphatics and oxygenated groups in soot particles decreased with the addition of methyl group(s) on the aromatic ring. The physicochemical changes in soot are found to support the oxidative reactivity trends. © 2016 The Combustion Institute

  5. Effects of methyl group on aromatic hydrocarbons on the nanostructures and oxidative reactivity of combustion-generated soot

    KAUST Repository

    Guerrero Peña, Gerardo D.J.

    2016-07-23

    The substituted and unsubstituted aromatic hydrocarbons, present in transportation fuels such as gasoline and diesel, are thought to be responsible for most of the soot particles produced during their combustion. However, the effects of the substituted alkyl groups on the aromatic hydrocarbons on their sooting tendencies, and on the physical and chemical properties of soot produced from them are not well understood. In this work, the effect of the presence of methyl groups on aromatic hydrocarbons on their sooting propensity, and on the oxidative reactivity, morphology, and chemical composition of soot generated from them in diffusion flames is studied using benzene, toluene, and m-xylene as fuels. Several experimental techniques including high resolution transmission electron microscopy and X-ray diffraction are used to identify the morphological changes in soot, whereas the elemental and thermo-gravimetric analyses, electron energy loss spectroscopy, and Fourier transform infrared spectroscopy are used to study the changes in its chemical properties and reactivity. The activation energies for soot oxidation are calculated at different conversion levels, and a trend in the reactivity of soots from benzene, toluene and m-xylene is reported. It is observed that the sizes of primary particles and graphene-like sheets, and the concentrations of aliphatics and oxygenated groups in soot particles decreased with the addition of methyl group(s) on the aromatic ring. The physicochemical changes in soot are found to support the oxidative reactivity trends. © 2016 The Combustion Institute

  6. The Reactive Species Interactome: Evolutionary Emergence, Biological Significance, and Opportunities for Redox Metabolomics and Personalized Medicine.

    Science.gov (United States)

    Cortese-Krott, Miriam M; Koning, Anne; Kuhnle, Gunter G C; Nagy, Peter; Bianco, Christopher L; Pasch, Andreas; Wink, David A; Fukuto, Jon M; Jackson, Alan A; van Goor, Harry; Olson, Kenneth R; Feelisch, Martin

    2017-10-01

    Oxidative stress is thought to account for aberrant redox homeostasis and contribute to aging and disease. However, more often than not, administration of antioxidants is ineffective, suggesting that our current understanding of the underlying regulatory processes is incomplete. Recent Advances: Similar to reactive oxygen species and reactive nitrogen species, reactive sulfur species are now emerging as important signaling molecules, targeting regulatory cysteine redox switches in proteins, affecting gene regulation, ion transport, intermediary metabolism, and mitochondrial function. To rationalize the complexity of chemical interactions of reactive species with themselves and their targets and help define their role in systemic metabolic control, we here introduce a novel integrative concept defined as the reactive species interactome (RSI). The RSI is a primeval multilevel redox regulatory system whose architecture, together with the physicochemical characteristics of its constituents, allows efficient sensing and rapid adaptation to environmental changes and various other stressors to enhance fitness and resilience at the local and whole-organism level. To better characterize the RSI-related processes that determine fluxes through specific pathways and enable integration, it is necessary to disentangle the chemical biology and activity of reactive species (including precursors and reaction products), their targets, communication systems, and effects on cellular, organ, and whole-organism bioenergetics using system-level/network analyses. Understanding the mechanisms through which the RSI operates will enable a better appreciation of the possibilities to modulate the entire biological system; moreover, unveiling molecular signatures that characterize specific environmental challenges or other forms of stress will provide new prevention/intervention opportunities for personalized medicine. Antioxid. Redox Signal. 00, 000-000.

  7. Chemical exchange effects in spectral line shapes

    International Nuclear Information System (INIS)

    Diaz, M.A.; Veguillas, J.

    1990-01-01

    A theory of spectral-line shapes has been extended to the case in which relaxation broadening may be influenced by reactive interactions. This extension is valid for gaseous systems in the same way it is valid for condensed media, and particularly, for such chemical mechanisms as isomerizations. The dependence of the spectral rate on the chemical exchange rate is clarified. Finally, a discussion concerning the above aspects and their applications has been included. (author)

  8. Improvement of COD and TOC reactive dyes in textile wastewater by ...

    African Journals Online (AJOL)

    STORAGESEVER

    2009-07-06

    Jul 6, 2009 ... This study was designed to investigate the removal of reactive dyes, Samofix Red V-RBL and Samofix. Green V-G from wastewater using a two step Al (III) coagulation/activated carbon adsorption method. ... (90%) of chemical oxygen demand (COD), total organic carbon (TOC) ..... a liquid to a solid surface.

  9. Reactivity III: An Advanced Course in Integrated Organic, Inorganic, and Biochemistry

    Science.gov (United States)

    Schaller, Chris P.; Graham, Kate J.; Jakubowski, Henry V.

    2017-01-01

    Reactivity III is a new course that presents chemical reactions from the domains of organic, inorganic, and biochemistry that are not readily categorized by electrophile-nucleophile interactions. Many of these reactions involve the transfer of a single electron, in either an intermolecular fashion in the case of oxidation/reduction reactions or an…

  10. Formation of Sulfonyl Aromatic Alcohols by Electrolysis of a Bisazo Reactive Dye

    Directory of Open Access Journals (Sweden)

    María P. Elizalde-González

    2012-12-01

    Full Text Available Five sulfonyl aromatic alcohols, namely 4-((2-hydroxyethylsulfonylphenol, 4-((2-(2-((4-hydroxyphenylsulfonylethoxyvinylsulfonylphenol, 4-(ethylsulfonylphenol, 4-(vinylsulfonylphenol and 5-((4-aminophenylsulfonyl-2-penten-1-ol were identified by LC-ESI-Qq-TOF-MS as products formed by electrolysis of the bisazo reactive dye Reactive Black 5 (RB5. Since electrolyses were performed in an undivided cell equipped with Ni electrodes in alkaline medium, amines like 4-(2-methoxyethylsulfonylbenzene-amine (MEBA with m/z 216 were also suspected to be formed due to the plausible chemical reaction in the bulk or the cathodic reduction of RB5 and its oxidation by-products. Aiming to check this hypothesis, a method was used for the preparation of MEBA with 98% purity, via chemical reduction also of the dye RB5. The logP of the synthesized sulfonyl aromatic compounds was calculated and their logkw values were determined chromatographically. These data were discussed in regard to the relationship between hydrophobicity/lipophilicity and toxicity.

  11. Stable isotope reactive transport modeling in water-rock interactions during CO2 injection

    Science.gov (United States)

    Hidalgo, Juan J.; Lagneau, Vincent; Agrinier, Pierre

    2010-05-01

    Stable isotopes can be of great usefulness in the characterization and monitoring of CO2 sequestration sites. Stable isotopes can be used to track the migration of the CO2 plume and identify leakage sources. Moreover, they provide unique information about the chemical reactions that take place on the CO2-water-rock system. However, there is a lack of appropriate tools that help modelers to incorporate stable isotope information into the flow and transport models used in CO2 sequestration problems. In this work, we present a numerical tool for modeling the transport of stable isotopes in groundwater reactive systems. The code is an extension of the groundwater single-phase flow and reactive transport code HYTEC [2]. HYTEC's transport module was modified to include element isotopes as separate species. This way, it is able to track isotope composition of the system by computing the mixing between the background water and the injected solution accounting for the dependency of diffusion on the isotope mass. The chemical module and database have been expanded to included isotopic exchange with minerals and the isotope fractionation associated with chemical reactions and mineral dissolution or precipitation. The performance of the code is illustrated through a series of column synthetic models. The code is also used to model the aqueous phase CO2 injection test carried out at the Lamont-Doherty Earth Observatory site (Palisades, New York, USA) [1]. References [1] N. Assayag, J. Matter, M. Ader, D. Goldberg, and P. Agrinier. Water-rock interactions during a CO2 injection field-test: Implications on host rock dissolution and alteration effects. Chemical Geology, 265(1-2):227-235, July 2009. [2] Jan van der Lee, Laurent De Windt, Vincent Lagneau, and Patrick Goblet. Module-oriented modeling of reactive transport with HYTEC. Computers & Geosciences, 29(3):265-275, April 2003.

  12. Reactive formulations for a neutralization of toxic industrial chemicals

    Science.gov (United States)

    Tucker, Mark D [Albuqueruqe, NM; Betty, Rita G [Rio Rancho, NM

    2006-10-24

    Decontamination formulations for neutralization of toxic industrial chemicals, and methods of making and using same. The formulations are effective for neutralizing malathion, hydrogen cyanide, sodium cyanide, butyl isocyanate, carbon disulfide, phosgene gas, capsaicin in commercial pepper spray, chlorine gas, anhydrous ammonia gas; and may be effective at neutralizing hydrogen sulfide, sulfur dioxide, formaldehyde, ethylene oxide, methyl bromide, boron trichloride, fluorine, tetraethyl pyrophosphate, phosphorous trichloride, arsine, and tungsten hexafluoride.

  13. Enhanced reactivation of UV-irradiated adenovirus 2 in HeLa cells treated with non-mutagenic chemical agents

    Energy Technology Data Exchange (ETDEWEB)

    Piperakis, S.M.; McLennan, A.G. (Liverpool Univ. (UK). Dept. of Biochemistry)

    1985-03-01

    Treatment of HeLa cells with ethanol and sodium arsenite, compounds which are known to elicit the heat-shock response, before infection with UV-irradiated adenovirus 2 has been found to result in the enhanced reactivation of the damaged virus in a manner similar to that obtained by pre-irradiation or heating of the cells. Enhanced reactivation may be the result of the inhibition of DNA synthesis caused by these agents since hydroxyurea also produced a significant enhancement.

  14. Enrichment of reactive macerals in coal: its characterization and utilization in coke making

    Science.gov (United States)

    Nag, Debjani; Kopparthi, P.; Dash, P. S.; Saxena, V. K.; Chandra, S.

    2018-01-01

    Macerals in coal are of different types: reactive and inert. These macerals are differ in their physical and chemical properties. Column flotation method has been used to separate the reactive macerals in a non-coking coal. The enriched coal is then characterized in order to understand the changes in the coking potential by different techniques. It is then used in making of metallurgical coke by proper blending with other coals. Enriched coal enhance the properties of metallurgical coke. This shows a path of utilization of non-coking coal in metallurgical coke making.

  15. Letter: Modeling reactive shock waves in heterogeneous solids at the continuum level with stochastic differential equations

    Science.gov (United States)

    Kittell, D. E.; Yarrington, C. D.; Lechman, J. B.; Baer, M. R.

    2018-05-01

    A new paradigm is introduced for modeling reactive shock waves in heterogeneous solids at the continuum level. Inspired by the probability density function methods from turbulent reactive flows, it is hypothesized that the unreacted material microstructures lead to a distribution of heat release rates from chemical reaction. Fluctuations in heat release, rather than velocity, are coupled to the reactive Euler equations which are then solved via the Riemann problem. A numerically efficient, one-dimensional hydrocode is used to demonstrate this new approach, and simulation results of a representative impact calculation (inert flyer into explosive target) are discussed.

  16. Computational simulation of reactive species production by methane-air DBD at high pressure and high temperature

    Science.gov (United States)

    Takana, H.; Tanaka, Y.; Nishiyama, H.

    2012-01-01

    Computational simulations of a single streamer in DBD in lean methane-air mixture at pressure of 1 and 3 atm and temperature of 300 and 500 K were conducted for plasma-enhanced chemical reactions in a closed system. The effects of surrounding pressure and temperature are characterized for reactive species production by a DBD discharge. The results show that the production characteristics of reactive species are strongly influenced by the total gas number density and the higher concentration of reactive species are produced at higher pressure and lower gas temperature for a given initial reduced electric field.

  17. Chemical Stimulation of Engineered Geothermal Systems

    Energy Technology Data Exchange (ETDEWEB)

    Rose, Peter, E.

    2008-08-08

    The objective of this project is to design, develop and demonstrate methods for the chemical stimulation of candidate EGS reservoirs as well as the chemical treatment of mineral-scaled wellbores. First, a set of candidate chemical compounds capable of dissolving calcite was identified. A series of tests was then performed on each candidate in order to screen it for thermal stability and reactivity towards calcite. A detailed analysis was then performed on each compound that emerged from the screening tests in order to characterize its decay kinetics and reaction kinetics as functions of temperature and chemical composition. From among the compounds emerging from the laboratory studies, one compounds was chosen for a field experiment in order to verify the laboratory predictions.

  18. Characterization and reactivity of sodium aluminoborosilicate glass fiber surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Ortiz Rivera, Lymaris, E-mail: luo105@psu.edu [Materials Research Institute, Pennsylvania State University, University Park, PA 16802 (United States); Bakaev, Victor A.; Banerjee, Joy [Materials Research Institute, Pennsylvania State University, University Park, PA 16802 (United States); Mueller, Karl T. [Department of Chemistry, Pennsylvania State University, University Park, PA 16802 (United States); Pantano, Carlo G. [Materials Research Institute, Pennsylvania State University, University Park, PA 16802 (United States); Department of Materials Science and Engineering, Pennsylvania State University, University Park, PA 16802 (United States)

    2016-05-01

    Highlights: • XPS revealed that these fiber surfaces contain sodium carbonate weathering products. • IGC–MS data confirms the products of acetic acid reaction with sodium carbonate. • NMR data shows two closely spaced, but distinct sodium carboxylate peaks. • Acetic acid reacts with both sodium in the glass and sodium in the sodium carbonate. - Abstract: Multicomponent complex oxides, such as sodium aluminoborosilicate glass fibers, are important materials used for thermal insulation in buildings and homes. Although the surface properties of single oxides, such as silica, have been extensively studied, less is known about the distribution of reactive sites at the surface of multicomponent oxides. Here, we investigated the reactivity of sodium aluminoborosilicate glass fiber surfaces for better understanding of their interface chemistry and bonding with acrylic polymers. Acetic acid (with and without a {sup 13}C enrichment) was used as a probe representative of the carboxylic functional groups in many acrylic polymers and adhesives. Inverse gas chromatography coupled to a mass spectrometer (IGC–MS), and solid state nuclear magnetic resonance (NMR), were used to characterize the fiber surface reactions and surface chemical structure. In this way, we discovered that both sodium ions in the glass surface, as well as sodium carbonate salts that formed on the surface due to the intrinsic reactivity of this glass in humid air, are primary sites of interaction with the carboxylic acid. Surface analysis by X-ray photoelectron spectroscopy (XPS) confirmed the presence of sodium carbonates on these surfaces. Computer simulations of the interactions between the reactive sites on the glass fiber surface with acetic acid were performed to evaluate energetically favorable reactions. The adsorption reactions with sodium in the glass structure provide adhesive bonding sites, whereas the reaction with the sodium carbonate consumes the acid to form sodium-carboxylate, H

  19. An indoor chemical cocktail

    Science.gov (United States)

    Gligorovski, Sasho; Abbatt, Jonathan P. D.

    2018-02-01

    In the past 50 years, many of the contaminants and chemical transformations that occur in outdoor waters, soils, and air have been elucidated. However, the chemistry of the indoor environment in which we live most of the time—up to 90% in some societies—is not nearly as well studied. Recent work has highlighted the wealth of chemical transformations that occur indoors. This chemistry is associated with 3 of the top 10 risk factors for negative health outcomes globally: household air pollution from solid fuels, tobacco smoking, and ambient particulate matter pollution (1). Assessments of human exposure to indoor pollutants must take these reactive processes into consideration.

  20. Tracing the plasma interactions for pulsed reactive crossed-beam laser ablation

    Science.gov (United States)

    Chen, Jikun; Stender, Dieter; Pichler, Markus; Döbeli, Max; Pergolesi, Daniele; Schneider, Christof W.; Wokaun, Alexander; Lippert, Thomas

    2015-10-01

    Pulsed reactive crossed-beam laser ablation is an effective technique to govern the chemical activity of plasma species and background molecules during pulsed laser deposition. Instead of using a constant background pressure, a gas pulse with a reactive gas, synchronized with the laser beam, is injected into vacuum or a low background pressure near the ablated area of the target. It intercepts the initially generated plasma plume, thereby enhancing the physicochemical interactions between the gaseous environment and the plasma species. For this study, kinetic energy resolved mass-spectrometry and time-resolved plasma imaging were used to study the physicochemical processes occurring during the reactive crossed beam laser ablation of a partially 18O substituted La0.6Sr0.4MnO3 target using oxygen as gas pulse. The characteristics of the ablated plasma are compared with those observed during pulsed laser deposition in different oxygen background pressures.

  1. Photoelectrochemical reactivity of polyoxophosphotungstates embedded in titania tubules

    International Nuclear Information System (INIS)

    Xie Yibing

    2006-01-01

    A highly ordered and crystallized titania (TiO 2 ) nanotube array is fabricated by a low-voltage anodization plus a post-embedding calcination process. Polyoxophosphotungstate-titania (POPTA-TiO 2 ) composite catalyst is synthesized by embedding POPTA in TiO 2 tubule channels to improve the photoelectrochemical properties. The morphological characteristics and crystal behaviour of POPTA-TiO 2 are examined by field-emission scanning electron microscopy and x-ray diffraction. The stability of the chemical structure has been analysed by Fourier transformed infrared spectroscopy measurements. The photoelectrochemical properties are investigated by means of the polarization current response. Photocatalytic and photoelectrocatalytic reactivities for the degradation of an endocrine disrupting chemical have also been investigated to examine the photoelectrochemical reaction efficiency of POPTA-TiO 2 composite catalyst

  2. Digital reactivity meter

    International Nuclear Information System (INIS)

    Akkus, B.; Anac, H.; Alsan, S.; Erk, S.

    1991-01-01

    Nowadays, various digital methods making use of microcomputers for neutron detector signals and determining the reactivity by numerical calculations are used in reactor control systems in place of classical reactivity meters. In this work, a calculation based on the ''The Time Dependent Transport Equation'' has been developed for determining the reactivity numerically. The reactivity values have been obtained utilizing a computer-based data acquisition and control system and compared with the analog reactivity meter values as well as the values calculated from the ''Inhour Equation''

  3. Yellow phosphorus process to convert toxic chemicals to non-toxic products

    Science.gov (United States)

    Chang, S.G.

    1994-07-26

    The present invention relates to a process for generating reactive species for destroying toxic chemicals. This process first contacts air or oxygen with aqueous emulsions of molten yellow phosphorus. This contact results in rapid production of abundant reactive species such as O, O[sub 3], PO, PO[sub 2], etc. A gaseous or liquid aqueous solution organic or inorganic chemicals is next contacted by these reactive species to reduce the concentration of toxic chemical and result in a non-toxic product. The final oxidation product of yellow phosphorus is phosphoric acid of a quality which can be recovered for commercial use. A process is developed such that the byproduct, phosphoric acid, is obtained without contamination of toxic species in liquids treated. A gas stream containing ozone without contamination of phosphorus containing species is also obtained in a simple and cost-effective manner. This process is demonstrated to be effective for destroying many types of toxic organic, or inorganic, compounds, including polychlorinated biphenyls (PCB), aromatic chlorides, amines, alcohols, acids, nitro aromatics, aliphatic chlorides, polynuclear aromatic compounds (PAH), dyes, pesticides, sulfides, hydroxyamines, ureas, dithionates and the like. 20 figs.

  4. Strength and Numerical Analysis in the Design of Permeable Reactive Barriers

    Science.gov (United States)

    Pawluk, Katarzyna; Wrzesiński, Grzegorz; Lendo-Siwicka, Marzena

    2017-10-01

    Permeable reactive barriers are one of the most important in situ technologies in groundwater remediation. Most of the installed PRBs have tended to use singular reactive media, but there is an increasing number of applications using combined or sequenced media to treat mixtures of contaminants within a groundwater plume. The concept of a multi-layered permeable reactive barrier (MPRB) to prevent and protect groundwater along traffic routes, especially in ecologically and naturally valuable areas, was developed following several field and laboratory investigations conducted in the Department of Geotechnical Engineering of the Warsaw University of Life Sciences. In accordance with the guidelines of the Interstate Technology & Regulatory Council for the selection of reactive materials, numerous laboratory and field investigations should be performed to determine the environmental conditions, type and concentrations of the contaminants, and the physical-chemical and permeability properties of the reactive materials. However, the deformation and strength properties of the reactive materials should be also considered in the design and evaluation of the safety conditions. In this paper, strength and deformation properties of silica spongolite, zeolite, and activated carbon were investigated using direct shear and oedometer tests. The laboratory test results were used in numerical calculations with the application of the finite element method. The aim of this study was to define the impact of the installation stages of a multi-layered permeable reactive barrier on the stability of a road embankment. Numerical analysis may prevent, reduce or eliminate the risk in the case of a breakdown during the construction or/and exploitation of a PRB.

  5. Effect of Strain on the Reactivity of Metal Surfaces

    DEFF Research Database (Denmark)

    Mavrikakis, Manos; Hammer, Bjørk; Nørskov, Jens Kehlet

    1998-01-01

    Self-consistent density functional calculations for the adsorption of O and CO, and the dissociation of CO on strained and unstrained Ru(0001) surfaces are used to show how strained metal surfaces have chemical properties that are significantly different from those of unstrained surfaces. Surface...... reactivity increases with lattice expansion, following a concurrent up-shift of the metal d states. Consequences for the catalytic activity of thin metal overlayers are discussed....

  6. Surface area and chemical reactivity characteristics of uranium metal corrosion products

    International Nuclear Information System (INIS)

    Totemeier, T. C.

    1998-01-01

    The results of an initial characterization of hydride-containing corrosion products from uranium metal Zero Power Physics Reactor (ZPPR) fuel plates are presented. Sorption analyses using the BET method with a Kr adsorbate were performed to measure the specific areas of corrosion product samples. The specific surface areas of the corrosion products varied from 0.66 to 1.01 m 2 /g. The reactivity of the products in Ar-9%O 2 and Ar-20%O 2 were measured at temperatures between 35 C and 150 C using a thermo-gravimetric analyzer. Ignition of the products occurred at temperatures of 150 C and above. The oxidation rates below ignition were comparable to rates observed for uranium metal

  7. Extension of a reactive distillation process design methodology: application to the hydrogen production through the Iodine-Sulfur thermochemical cycle; Generalisation d'une approche de conception de procedes de distillation reactive: application a la production d'hydrogene par le cycle thermochimique I-S

    Energy Technology Data Exchange (ETDEWEB)

    Belaissaoui, B

    2006-02-15

    Reactive distillation is a promising way to improve classical processes. This interest has been comforted by numerous successful applications involving reactive systems in liquid phase but never in vapour phase. In this context, general design tools have been developed for the analysis of reactive distillation processes whatever the reactive phase. A general model for open condensation and evaporation of vapour or liquid reactive systems in chemical equilibrium has been written and applied to extend the feasibility analysis, synthesis and design methods of the sequential design methodology of R. Thery (2002). The extended design methodology is applied to the industrial production of hydrogen through the iodine-sulphur thermochemical cycle by vapour phase reactive distillation. A column configuration is proposed with better performance formerly published configuration. (author)

  8. Diazo Compounds: Versatile Tools for Chemical Biology.

    Science.gov (United States)

    Mix, Kalie A; Aronoff, Matthew R; Raines, Ronald T

    2016-12-16

    Diazo groups have broad and tunable reactivity. That and other attributes endow diazo compounds with the potential to be valuable reagents for chemical biologists. The presence of diazo groups in natural products underscores their metabolic stability and anticipates their utility in a biological context. The chemoselectivity of diazo groups, even in the presence of azido groups, presents many opportunities. Already, diazo compounds have served as chemical probes and elicited novel modifications of proteins and nucleic acids. Here, we review advances that have facilitated the chemical synthesis of diazo compounds, and we highlight applications of diazo compounds in the detection and modification of biomolecules.

  9. Detection of Pesticides and Pesticide Metabolites Using the Cross Reactivity of Enzyme Immunoassays

    Science.gov (United States)

    Thurman, E.M.; Aga, D.S.

    2001-01-01

    Enzyme immunoassay is an important environmental analysis method that may be used to identify many pesticide analytes in water samples. Because of similarities in chemical structure between various members of a pesticide class, there often may be an unwanted response that is characterized by a percentage of cross reactivity. Also, there may be cross reactivity caused by degradation products of the target analyte that may be present in the sample. In this paper, the concept of cross reactivity caused by degradation products or by nontarget analytes is explored as a tool for identification of metabolites or structurally similar compounds not previously known to be present in water samples. Two examples are examined in this paper from various water quality studies. They are alachlor and its metabolite, alachlor ethane sulfonic acid, and atrazine and its class members, prometryn and propazine. A method for using cross reactivity for the detection of these compounds is explained in this paper.

  10. Chemically reactive and naturally convective high speed MHD fluid flow through an oscillatory vertical porous plate with heat and radiation absorption effect

    Directory of Open Access Journals (Sweden)

    S.M. Arifuzzaman

    2018-04-01

    Full Text Available This paper concerns with the modelling of an unsteady natural convective and higher order chemically reactive magnetohydrodynamics (MHD fluid flow with the effect of heat and radiation absorption. The flow is generated through a vertical oscillating porous plate. Boundary layer approximations is carried out to establish a flow model which represents the time dependent momentum, energy and diffusion balance equations. Before being solved numerically, the governing partial differential equations (PDEs were transformed into a set of nonlinear ordinary differential equation (ODEs by using non-similar technique. A very efficient numerical approach solves the obtained nonlinear coupled ODEs so called Explicit Finite Difference Method (EFDM. An algorithm is implemented in Compaq Visual Fortran 6.6a as a solving tool. In addition, the stability and convergence analysis (SCA is examined and shown explicitly. The advantages of SCA is its optimizes the accuracy of system parameters such as Prandtl number (Pr and Schmidt number (Sc.The velocity, temperature and concentration fields in the boundary layer region are studied in detail and the outcomes are shown in graphically with the influence of various pertinent parameters such as Grashof number (Gr, modified Grashof number (Gr, magnetic parameter (M, Darcy number (Da,Prandtl number (Pr, Schmidt number (Sc, radiation (R, heat sink (Q,radiation absorption (Q1, Eckert number (Ec, Dufour number (Du,Soret number (Sr, Schmidt number (Sc, reaction index (P and chemical reaction (Kr. Furthermore, the effect of skin friction coefficient (Cf, Nusselt number (Nu and Sherwood number (Sh are also examined graphically. Keywords: MHD, Oscillating porous plate, Radiation absorption, High order chemical reaction, EFDM

  11. Journal of Chemical Sciences | Indian Academy of Sciences

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 126; Issue 5. A Reactive Intermediate, [Ni5(C6H4N3)6(CO)4], in the Formation of Nonameric Clusters of Nickel, [Ni9(C6H4N3)12(CO)6] and [Ni9(C6H4N3)12(CO)6].2(C3H7NO). Subhradeep Mistry Srinivasan Natarajan. Special issue on Chemical Crystallography ...

  12. Opportunities for Merging Chemical and Biological Synthesis

    Science.gov (United States)

    Wallace, Stephen; Balskus, Emily P.

    2014-01-01

    Organic chemists and metabolic engineers use largely orthogonal technologies to access small molecules like pharmaceuticals and commodity chemicals. As the use of biological catalysts and engineered organisms for chemical production grows, it is becoming increasingly evident that future efforts for chemical manufacture will benefit from the integration and unified expansion of these two fields. This review will discuss approaches that combine chemical and biological synthesis for small molecule production. We highlight recent advances in combining enzymatic and non-enzymatic catalysis in vitro, discuss the application of design principles from organic chemistry for engineering non-biological reactivity into enzymes, and describe the development of biocompatible chemistry that can be interfaced with microbial metabolism. PMID:24747284

  13. Chemical composition of wildland fire emissions

    Science.gov (United States)

    Shawn P. Urbanski; Wei Min Hao; Stephen Baker

    2009-01-01

    Wildland fires are major sources of trace gases and aerosol, and these emissions are believed to significantly influence the chemical composition of the atmosphere and the earth's climate system. The wide variety of pollutants released by wildland fire include greenhouse gases, photochemically reactive compounds, and fine and coarse particulate matter. Through...

  14. Development of photopolymerizable clay nanocomposites utilizing reactive dispersants

    Science.gov (United States)

    Owusu-Adom, Kwame

    Nanocomposites hold tremendous promise for expanding the utility of polymeric materials. However, accessing particulate sizes in the nanoscale domain continues to be a scientific challenge, especially in highly cross-linked photopolymerizable systems. In this study, photopolymerizable nanocomposites utilizing clay nanoparticles and reactive dispersants have been developed. The influence of particle size, dispersant-clay interactions, and surfactant concentration on photopolymerization behavior and nanoparticle dispersion has been elucidated. Clay particles serve as templates upon which surfactants aggregate during photopolymerization. This results in higher photopolymerization rates with addition of increasing concentrations of polymerizable surfactants. Furthermore, polymerizable surfactants induce faster photopolymerization rates compared to non-polymerizable analogues in systems that have ionically-bound dispersants on the particle surface. Utilizing reactive organoclays induces significant changes to the photopolymerization behavior depending on the choice of reactive functionality employed. Faster acrylate photopolymerization rates occur in photopolymer systems containing thiol-modified clays, while much slower rates occur for nonpolymerizable organoclay systems. In addition, chemical compatibility between monomer and clay dispersant (based on chemical similarity or polarity) allows enhancement of exfoliation in photopolymerizable formulations. With polymerizable dispersants, exfoliation is readily achieved in various multifunctional acrylate systems. The degree of exfoliation depends on the position of the reactive group relative to the surfactant's cationic site and the type of functionality. Thiolated organoclays exfoliate during polymerization, while methacrylated clays show substantially less dependence on polymerization behavior. Interestingly, changes in the physical properties of the resulting nanocomposite are independent of the degree of exfoliation

  15. Chemical and Photochemical Reactivity in Microemulsions and Waterless Microemulsions.

    Science.gov (United States)

    1988-02-10

    virtually the same as that found in the alcohol rich microemulsion A. This value is also close to that found in pure butanol (= 5.0 - table I). It would...formamide or alcohol rich). RESEARCH PATTERN -Supplementing the physical chemical study of the microemulsion medium involving ionic surfactants with density...SAMII (1/02/1988) Ii&N 3 Part II - OXYDATIONS BY HYDROPEROXIDES IN MICROEMULSIONS E. OLIVEROS and M.T. MAURETTE During the past six months, the financial

  16. A density functional theory-based chemical potential equalisation ...

    Indian Academy of Sciences (India)

    Unknown

    ties both of which can be calculated through the evaluation of ... used widely for the understanding of chemical binding, reactivity ... lent binding. There have ..... where ε represents a measure of the dielectric con- stant of the ..... field strength.

  17. Calcium oxide/carbon dioxide reactivity in a packed bed reactor of a chemical heat pump for high-temperature gas reactors

    International Nuclear Information System (INIS)

    Kato, Yukitaka; Yamada, Mitsuteru; Kanie, Toshihiro; Yoshizawa, Yoshio

    2001-01-01

    The thermal performance of a chemical heat pump that uses a calcium oxide/carbon dioxide reaction system was discussed as a heat storage system for utilizing heat output from high temperature gas reactors (HTGR). Calcium oxide/carbon dioxide reactivity for the heat pump was measured using a packed bed reactor containing 1.0 kg of reactant. The reactor was capable of storing heat at 900 deg. C by decarbonation of calcium carbonate and generating up to 997 deg. C by carbonation of calcium oxide. The amount of stored heat in the reactor was 800-900 kJ kg -1 . The output temperature of the reactor could be controlled by regulating the carbonation pressure. The thermal storage performance of the reactor was superior to that of conventional sensible heat storage systems. A heat pump using this CaO/CO 2 reactor is expected to contribute to thermal load leveling and to realize highly efficient utilization of HTGR output due to the high heat storage density and high-quality temperature output of the heat pump

  18. Development of numerical methods for reactive transport

    International Nuclear Information System (INIS)

    Bouillard, N.

    2006-12-01

    When a radioactive waste is stored in deep geological disposals, it is expected that the waste package will be damaged under water action (concrete leaching, iron corrosion). Then, to understand these damaging processes, chemical reactions and solutes transport are modelled. Numerical simulations of reactive transport can be done sequentially by the coupling of several codes. This is the case of the software platform ALLIANCES which is developed jointly with CEA, ANDRA and EDF. Stiff reactions like precipitation-dissolution are crucial for the radioactive waste storage applications, but standard sequential iterative approaches like Picard's fail in solving rapidly reactive transport simulations with such stiff reactions. In the first part of this work, we focus on a simplified precipitation and dissolution process: a system made up with one solid species and two aqueous species moving by diffusion is studied mathematically. It is assumed that a precipitation dissolution reaction occurs in between them, and it is modelled by a discontinuous kinetics law of unknown sign. By using monotonicity properties, the convergence of a finite volume scheme on admissible mesh is proved. Existence of a weak solution is obtained as a by-product of the convergence of the scheme. The second part is dedicated to coupling algorithms which improve Picard's method and can be easily used in an existing coupling code. By extending previous works, we propose a general and adaptable framework to solve nonlinear systems. Indeed by selecting special options, we can either recover well known methods, like nonlinear conjugate gradient methods, or design specific method. This algorithm has two main steps, a preconditioning one and an acceleration one. This algorithm is tested on several examples, some of them being rather academical and others being more realistic. We test it on the 'three species model'' example. Other reactive transport simulations use an external chemical code CHESS. For a

  19. Composition and optical properties tunability of hydrogenated silicon carbonitride thin films deposited by reactive magnetron sputtering

    Science.gov (United States)

    Bachar, A.; Bousquet, A.; Mehdi, H.; Monier, G.; Robert-Goumet, C.; Thomas, L.; Belmahi, M.; Goullet, A.; Sauvage, T.; Tomasella, E.

    2018-06-01

    Radiofrequency reactive magnetron sputtering was used to deposit hydrogenated amorphous silicon carbonitride (a-SiCxNy:H) at 400 °C by sputtering a silicon target under CH4 and N2 reactive gas mixture. Rutherford backscattering spectrometry revealed that the change of reactive gases flow rate (the ratio R = FN2/(FN2+FCH4)) induced a smooth chemical composition tunability from a silicon carbide-like film for R = 0 to a silicon nitride-like one at R = 1 with a large area of silicon carbonitrides between the two regions. The deconvolution of Fourier Transform InfraRed and X-ray photoelectron spectroscopy spectrum highlighted a shift of the chemical environment of the deposited films corresponding to the changes seen by RBS. The consequence of these observations is that a control of refractive index in the range of [1.9-2.5] at λ = 633 nm and optical bandgap in the range [2 eV-3.8 eV] have been obtained which induces that these coatings can be used as antireflective coatings in silicon photovoltaic cells.

  20. Modeling turbulence structure. Chemical kinetics interaction in turbulent reactive flows

    Energy Technology Data Exchange (ETDEWEB)

    Magnussen, B F [The Norwegian Univ. of Science and Technology, Trondheim (Norway)

    1998-12-31

    The challenge of the mathematical modelling is to transfer basic physical knowledge into a mathematical formulation such that this knowledge can be utilized in computational simulation of practical problems. The combustion phenomena can be subdivided into a large set of interconnected phenomena like flow, turbulence, thermodynamics, chemical kinetics, radiation, extinction, ignition etc. Combustion in one application differs from combustion in another area by the relative importance of the various phenomena. The difference in fuel, geometry and operational conditions often causes the differences. The computer offers the opportunity to treat the individual phenomena and their interactions by models with wide operational domains. The relative magnitude of the various phenomena therefore becomes the consequence of operational conditions and geometry and need not to be specified on the basis of experience for the given problem. In mathematical modelling of turbulent combustion, one of the big challenges is how to treat the interaction between the chemical reactions and the fluid flow i.e. the turbulence. Different scientists adhere to different concepts like the laminar flamelet approach, the pdf approach of the Eddy Dissipation Concept. Each of these approaches offers different opportunities and problems. All these models are based on a sound physical basis, however none of these have general validity in taking into consideration all detail of the physical chemical interaction. The merits of the models can only be judged by their ability to reproduce physical reality and consequences of operational and geometric conditions in a combustion system. The presentation demonstrates and discusses the development of a coherent combustion technology for energy conversion and safety based on the Eddy Dissipation Concept by Magnussen. (author) 30 refs.

  1. Modeling turbulence structure. Chemical kinetics interaction in turbulent reactive flows

    Energy Technology Data Exchange (ETDEWEB)

    Magnussen, B.F. [The Norwegian Univ. of Science and Technology, Trondheim (Norway)

    1997-12-31

    The challenge of the mathematical modelling is to transfer basic physical knowledge into a mathematical formulation such that this knowledge can be utilized in computational simulation of practical problems. The combustion phenomena can be subdivided into a large set of interconnected phenomena like flow, turbulence, thermodynamics, chemical kinetics, radiation, extinction, ignition etc. Combustion in one application differs from combustion in another area by the relative importance of the various phenomena. The difference in fuel, geometry and operational conditions often causes the differences. The computer offers the opportunity to treat the individual phenomena and their interactions by models with wide operational domains. The relative magnitude of the various phenomena therefore becomes the consequence of operational conditions and geometry and need not to be specified on the basis of experience for the given problem. In mathematical modelling of turbulent combustion, one of the big challenges is how to treat the interaction between the chemical reactions and the fluid flow i.e. the turbulence. Different scientists adhere to different concepts like the laminar flamelet approach, the pdf approach of the Eddy Dissipation Concept. Each of these approaches offers different opportunities and problems. All these models are based on a sound physical basis, however none of these have general validity in taking into consideration all detail of the physical chemical interaction. The merits of the models can only be judged by their ability to reproduce physical reality and consequences of operational and geometric conditions in a combustion system. The presentation demonstrates and discusses the development of a coherent combustion technology for energy conversion and safety based on the Eddy Dissipation Concept by Magnussen. (author) 30 refs.

  2. Solar light-induced production of reactive oxygen species by single walled carbon nanotubes in water

    Science.gov (United States)

    Photosensitizing processes of engineered nanomaterials (ENMs) which include photo-induced production of reactive oxygen species (ROS) convert light energy into oxidizing chemical energy that mediates transformations of nanomaterials. The oxidative stress associated with ROS may p...

  3. Surface area and chemical reactivity characteristics of uranium metal corrosion products.

    Energy Technology Data Exchange (ETDEWEB)

    Totemeier, T. C.

    1998-02-17

    The results of an initial characterization of hydride-containing corrosion products from uranium metal Zero Power Physics Reactor (ZPPR) fuel plates are presented. Sorption analyses using the BET method with a Kr adsorbate were performed to measure the specific areas of corrosion product samples. The specific surface areas of the corrosion products varied from 0.66 to 1.01 m{sup 2}/g. The reactivity of the products in Ar-9%O{sub 2} and Ar-20%O{sub 2} were measured at temperatures between 35 C and 150 C using a thermo-gravimetric analyzer. Ignition of the products occurred at temperatures of 150 C and above. The oxidation rates below ignition were comparable to rates observed for uranium metal.

  4. Acoustic sensors for the control of liquid-solid interface evolution and chemical reactivity

    International Nuclear Information System (INIS)

    Ferrandis, J.Y.; Tingry, S.; Attal, J.; Seta, P.

    2006-01-01

    Less classical than far-field acoustic investigations of solid materials and/or solid-liquid interfaces, near-field acoustic properties of an acoustic solid wave guide (tip), thin enough at its termination to present an external diameter smaller than the excitation acoustic wave wavelength, is shown to be able to probe interface properties. As a result of that, these near-field acoustic probes can play the role of chemical sensors, if chemical modifications or chemical reactions are concerned at their surface. In that context, a chemical sensor was realized by electrochemical deposition of an electron-conducting polymer (polypyrrole-biotin) on a metal tip, followed by enzyme attachment by molecular recognition process involving the biotin-avidin-specific interaction. Results from near-field acoustic showed that the enzyme modification of the polymer layer can be detected by this new acoustic sensor

  5. Tracing the plasma interactions for pulsed reactive crossed-beam laser ablation

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Jikun; Stender, Dieter; Pichler, Markus; Pergolesi, Daniele; Schneider, Christof W.; Wokaun, Alexander; Lippert, Thomas, E-mail: thomas.lippert@psi.ch [General Energy Research Department, Paul Scherrer Institute, CH-5232 Villigen PSI (Switzerland); Döbeli, Max [Ion Beam Physics, ETH Zurich, CH-8093 Zurich (Switzerland)

    2015-10-28

    Pulsed reactive crossed-beam laser ablation is an effective technique to govern the chemical activity of plasma species and background molecules during pulsed laser deposition. Instead of using a constant background pressure, a gas pulse with a reactive gas, synchronized with the laser beam, is injected into vacuum or a low background pressure near the ablated area of the target. It intercepts the initially generated plasma plume, thereby enhancing the physicochemical interactions between the gaseous environment and the plasma species. For this study, kinetic energy resolved mass-spectrometry and time-resolved plasma imaging were used to study the physicochemical processes occurring during the reactive crossed beam laser ablation of a partially {sup 18}O substituted La{sub 0.6}Sr{sub 0.4}MnO{sub 3} target using oxygen as gas pulse. The characteristics of the ablated plasma are compared with those observed during pulsed laser deposition in different oxygen background pressures.

  6. A reactive empirical bond order (REBO) potential for hydrocarbon-oxygen interactions

    International Nuclear Information System (INIS)

    Ni, Boris; Lee, Ki-Ho; Sinnott, Susan B

    2004-01-01

    The expansion of the second-generation reactive empirical bond order (REBO) potential for hydrocarbons, as parametrized by Brenner and co-workers, to include oxygen is presented. This involves the explicit inclusion of C-O, H-O, and O-O interactions to the existing C-C, C-H, and H-H interactions in the REBO potential. The details of the expansion, including all parameters, are given. The new, expanded potential is then applied to the study of the structure and chemical stability of several molecules and polymer chains, and to modelling chemical reactions among a series of molecules, within classical molecular dynamics simulations

  7. Kinetic and mechanistic studies of reactive intermediates in photochemical and transition metal-assisted oxidation, decarboxylation and alkyl transfer reactions

    Energy Technology Data Exchange (ETDEWEB)

    Carraher, Jack McCaslin [Iowa State Univ., Ames, IA (United States)

    2014-01-01

    Reactive species like high-valent metal-oxo complexes and carbon and oxygen centered radicals are important intermediates in enzymatic systems, atmospheric chemistry, and industrial processes. Understanding the pathways by which these intermediates form, their relative reactivity, and their fate after reactions is of the utmost importance. Herein are described the mechanistic detail for the generation of several reactive intermediates, synthesis of precursors, characterization of precursors, and methods to direct the chemistry to more desirable outcomes yielding ‘greener’ sources of commodity chemicals and fuels.

  8. Dependence of energy per molecule on sputtering yields with reactive gas cluster ions

    International Nuclear Information System (INIS)

    Toyoda, Noriaki; Yamada, Isao

    2010-01-01

    Gas cluster ions show dense energy deposition on a target surface, which result in the enhancement of chemical reactions. In reactive sputtering with gas cluster ions, the energy per atom or molecule plays an important role. In this study, the average cluster size (N, the number of atoms or molecules in a cluster ion) was controlled; thereby the dependences of the energy per molecule on the sputtering yields of carbon by CO 2 cluster ions and that of Si by SF 6 /Ar mixed gas cluster ions were investigated. Large CO 2 cluster ions with energy per molecule of 1 eV showed high reactive sputtering yield of an amorphous carbon film. However, these ions did not cause the formation of large craters on a graphite surface. It is possible to achieve very low damage etching by controlling the energy per molecule of reactive cluster ions. Further, in the case of SF 6 /Ar mixed cluster ions, it was found that reactive sputtering was enhanced when a small amount of SF 6 gas (∼10%) was mixed with Ar. The reactive sputtering yield of Si by one SF 6 molecule linearly increased with the energy per molecule.

  9. Reactive simulation of the chemistry behind the condensed-phase ignition of RDX from hot spots.

    Science.gov (United States)

    Joshi, Kaushik L; Chaudhuri, Santanu

    2015-07-28

    Chemical events that lead to thermal initiation and spontaneous ignition of the high-pressure phase of RDX are presented using reactive molecular dynamics simulations. In order to initiate the chemistry behind thermal ignition, approximately 5% of RDX crystal is subjected to a constant temperature thermal pulse for various time durations to create a hot spot. After application of the thermal pulse, the ensuing chemical evolution of the system is monitored using reactive molecular dynamics under adiabatic conditions. Thermal pulses lasting longer than certain time durations lead to the spontaneous ignition of RDX after an incubation period. For cases where the ignition is observed, the incubation period is dominated by intermolecular and intramolecular hydrogen transfer reactions. Contrary to the widely accepted unimolecular models of initiation chemistry, N-N bond dissociations that produce NO2 species are suppressed in the condensed phase. The gradual temperature and pressure increase in the incubation period is accompanied by the accumulation of short-lived, heavier polyradicals. The polyradicals contain intact triazine rings from the RDX molecules. At certain temperatures and pressures, the polyradicals undergo ring-opening reactions, which fuel a series of rapid exothermic chemical reactions leading to a thermal runaway regime with stable gas-products such as N2, H2O and CO2. The evolution of the RDX crystal throughout the thermal initiation, incubation and thermal runaway phases observed in the reactive simulations contains a rich diversity of condensed-phase chemistry of nitramines under high-temperature/pressure conditions.

  10. Functionalization of whey proteins by reactive supercritical fluid extrusion

    Directory of Open Access Journals (Sweden)

    Khanitta Ruttarattanamongkol

    2012-09-01

    Full Text Available Whey protein, a by-product from cheese-making, is often used in a variety of food formulations due to its unsurpassednutritional quality and inherent functional properties. However, the possibilities for the improvement and upgrading of wheyprotein utilization still need to be explored. Reactive supercritical fluid extrusion (SCFX is a novel technique that has beenrecently reported to successfully functionalize commercially available whey proteins into a product with enhanced functionalproperties. The specific goal of this review is to provide fundamental understanding of the reinforcement mechanism andprocessing of protein functionalization by reactive SCFX process. The superimposed extrusion variables and their interactionmechanism affect the physico-chemical properties of whey proteins. By understanding the structure, functional properties andprocessing relationships of such materials, the rational design criteria for novel functionalized proteins could be developedand effectively utilized in food systems.

  11. 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

  12. 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

  13. From simple to complex and backwards. Chemical reactions under very high pressure

    International Nuclear Information System (INIS)

    Bini, Roberto; Ceppatelli, Matteo; Citroni, Margherita; Schettino, Vincenzo

    2012-01-01

    Highlights: ► High pressure reactivity of several molecular systems. ► Reaction kinetics and dynamics in high density conditions. ► Key role of optical pumping and electronic excitation. ► Perspectives for the synthesis of hydrogen. - Abstract: High pressure chemical reactions of molecular systems are discussed considering the various factors that can affect the reactivity. These include steric hindrance and geometrical constraints in the confined environment of crystals at high pressure, changes of the free energy landscape with pressure, photoactivation by two-photon absorption, local and collective effects. A classification of the chemical reactions at high pressure is attempted on the basis of the prevailing factors.

  14. The water-soluble fraction of potentially toxic elements in contaminated soils: relationships between ecotoxicity, solubility and geochemical reactivity.

    Science.gov (United States)

    Rocha, L; Rodrigues, S M; Lopes, I; Soares, A M V M; Duarte, A C; Pereira, E

    2011-09-01

    To better understand the impacts posed by soil contamination to aquatic ecosystems it is crucial to characterise the links between ecotoxicity, chemical availability and geochemical reactivity of potentially toxic elements (PTE's) in soils. We evaluated the adverse effects of water extracts obtained from soils contaminated by chemical industry and mining, using a test battery including organisms from different trophic levels (bacteria, algae and daphnids). These tests provided a quick assessment of the ecotoxicity of soils with respect to possible adverse effects on aquatic organisms although the ecotoxicological responses could be related to the solubility of PTE's only to a limited extent. The analysis of results of bioassays together with the chemical characterisation of water extracts provided additional relevant insight into the role of conductivity, pH, Al, Fe, and Mn of soil extracts on toxicity to organisms. Furthermore, an important conclusion of this study was that the toxicity of extracts to the aquatic organisms could also be related to the soil properties (pH, Org C and Fe(ox)) and to the reactivity of PTE's in soils which in fact control the soluble fraction of the contaminants. The combined assessment of ecotoxicity in water fractions, solubility and geochemical reactivity of PTE's in soils provided a more comprehensive understanding of the bioavailability of inorganic contaminants than ecotoxicological or chemical studies alone and can therefore be most useful for environmental risks assessment of contaminated soils. Copyright © 2011 Elsevier Ltd. All rights reserved.

  15. Reactive sputter deposition of boron nitride

    International Nuclear Information System (INIS)

    Jankowski, A.F.; Hayes, J.P.; McKernan, M.A.; Makowiecki, D.M.

    1995-10-01

    The preparation of fully dense, boron targets for use in planar magnetron sources has lead to the synthesis of Boron Nitride (BN) films by reactive rf sputtering. The deposition parameters of gas pressure, flow and composition are varied along with substrate temperature and applied bias. The films are characterized for composition using Auger electron spectroscopy, for chemical bonding using Raman spectroscopy and for crystalline structure using transmission electron microscopy. The deposition conditions are established which lead to the growth of crystalline BN phases. In particular, the growth of an adherent cubic BN coating requires 400--500 C substrate heating and an applied -300 V dc bias

  16. Gas phase reactive collisions, experimental approach

    Directory of Open Access Journals (Sweden)

    Canosa A.

    2012-01-01

    Full Text Available Since 1937 when the first molecule in space has been identified, more than 150 molecules have been detected. Understanding the fate of these molecules requires having a perfect view of their photochemistry and reactivity with other partners. It is then crucial to identify the main processes that will produce and destroy them. In this chapter, a general view of experimental techniques able to deliver gas phase chemical kinetics data at low and very low temperatures will be presented. These techniques apply to the study of reactions between neutral reactants on the one hand and reactions involving charge species on the other hand.

  17. Ionic liquids: radiation chemistry, solvation dynamics and reactivity patterns

    International Nuclear Information System (INIS)

    Wishart, J.F.; Funston, A.M.; Szreder, T.

    2006-01-01

    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 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 energy production, chemical industry and environmental applications. Pulse radiolysis of [R 4 N][NTf 2 ] [R 4 N][N(CN) 2 ], and [R 4 P][N(CN) 2 ] ionic liquids produces solvated electrons that absorb over a broad range in the near infrared and persisting for hundreds of nanoseconds. Systematic cation variation shows that solvated electron's spectroscopic properties depend strongly on the lattice structure of the ionic liquid. Very early in our radiolysis studies it became evident that

  18. Can hydroxylamine be a more potent nucleophile for the reactivation of tabun-inhibited AChE than prototype oxime drugs? An answer derived from quantum chemical and steered molecular dynamics studies.

    Science.gov (United States)

    Lo, Rabindranath; Ganguly, Bishwajit

    2014-07-29

    Organophosphorus nerve agents are highly toxic compounds which strongly inhibit acetylcholinesterase (AChE) in the blood and in the central nervous system (CNS). Tabun is one of the highly toxic organophosphorus (OP) compounds and is resistant to many oxime drugs formulated for the reactivation of AChE. The reactivation mechanism of tabun-conjugated AChE with various drugs has been examined with density functional theory and ab initio quantum chemical calculations. The presence of a lone-pair located on the amidic group resists the nucleophilic attack at the phosphorus center of the tabun-conjugated AChE. We have shown that the newly designed drug candidate N-(pyridin-2-yl)hydroxylamine, at the MP2/6-31+G*//M05-2X/6-31G* level in the aqueous phase with the polarizable continuum solvation model (PCM), is more effective in reactivating the tabun-conjugated AChE than typical oxime drugs. The rate determining activation barrier with N-(pyridin-2-yl)hydroxylamine was found to be ∼1.7 kcal mol(-1), which is 7.2 kcal mol(-1) lower than the charged oxime trimedoxime (one of the most efficient reactivators in tabun poisonings). The greater nucleophilicity index (ω(-)) and higher CHelpG charge of pyridinylhydroxylamine compared to TMB4 support this observation. Furthermore, we have also examined the reactivation process of tabun-inhibited AChE with some other bis-quaternary oxime drug candidates such as methoxime (MMB4) and obidoxime. The docking analysis suggests that charged bis-quaternary pyridinium oximes have greater binding affinity inside the active-site gorge of AChE compared to the neutral pyridinylhydroxylamine. The peripheral ligand attached to the neutral pyridinylhydroxylamine enhanced the binding with the aromatic residues in the active-site gorge of AChE through effective π-π interactions. Steered molecular dynamics (SMD) simulations have also been performed with the charged oxime (TMB4) and the neutral hydroxylamine. From protein-drug interaction

  19. Journal of Chemical Sciences | Indian Academy of Sciences

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 117; Issue 5. Application of localized reactivity index in combination with periodic DFT calculation to rationalize the swelling mechanism of clay type inorganic material. Abhijit Chatterjee. Volume 117 Issue 5 September 2005 pp 533-539 ...

  20. Journal of Chemical Sciences | Indian Academy of Sciences

    Indian Academy of Sciences (India)

    The chemical reactivity descriptors, such as electronegativity, hardness and electrophilicity of major oxides computed from density functional theory are reported in this paper. These parameters are plotted within a fitness landscape diagram, showing that the principles of minimum electrophilicity (MEP) and maximum ...

  1. Surface properties of hydrogenated nanodiamonds: a chemical investigation.

    Science.gov (United States)

    Girard, H A; Petit, T; Perruchas, S; Gacoin, T; Gesset, C; Arnault, J C; Bergonzo, P

    2011-06-28

    Hydrogen terminations (C-H) confer to diamond layers specific surface properties such as a negative electron affinity and a superficial conductive layer, opening the way to specific functionalization routes. For example, efficient covalent bonding of diazonium salts or of alkene moieties can be performed on hydrogenated diamond thin films, owing to electronic exchanges at the interface. Here, we report on the chemical reactivity of fully hydrogenated High Pressure High Temperature (HPHT) nanodiamonds (H-NDs) towards such grafting, with respect to the reactivity of as-received NDs. Chemical characterizations such as FTIR, XPS analysis and Zeta potential measurements reveal a clear selectivity of such couplings on H-NDs, suggesting that C-H related surface properties remain dominant even on particles at the nanoscale. These results on hydrogenated NDs open up the route to a broad range of new functionalizations for innovative NDs applications development. This journal is © the Owner Societies 2011

  2. BN600 reactivity definition

    International Nuclear Information System (INIS)

    Zheltyshev, V.; Ivanov, A.

    2000-01-01

    Since 1980, the fast BN600 reactor with sodium coolant has been operated at Beloyarsk Nuclear Power Plant. The periodic monitoring of the reactivity modifications should be implemented in compliance with the standards and regulations applied in nuclear power engineering. The reactivity measurements are carried out in order to confirm the basic neutronic features of a BN600 reactor. The reactivity measurements are aimed to justify that nuclear safety is provided in course of the in-reactor installation of the experimental core components. Two reactivity meters are to be used on BN600 operation: 1. Digital on-line reactivity calculated under stationary reactor operation on power (approximation of the point-wise kinetics is applied). 2. Second reactivity meter used to define the reactor control rod operating components efficiency under reactor startup and take account of the changing efficiency of the sensor, however, this is more time-consumptive than the on-line reactivity meter. The application of two reactivity meters allows for the monitoring of the reactor reactivity under every operating mode. (authors)

  3. Sensing and tactile artificial muscles from reactive materials.

    Science.gov (United States)

    Conzuelo, Laura Valero; Arias-Pardilla, Joaquín; Cauich-Rodríguez, Juan V; Smit, Mascha Afra; Otero, Toribio Fernández

    2010-01-01

    Films of conducting polymers can be oxidized and reduced in a reversible way. Any intermediate oxidation state determines an electrochemical equilibrium. Chemical or physical variables acting on the film may modify the equilibrium potential, so that the film acts as a sensor of the variable. The working potential of polypyrrole/DBSA (Dodecylbenzenesulfonic acid) films, oxidized or reduced under constant currents, changes as a function of the working conditions: electrolyte concentration, temperature or mechanical stress. During oxidation, the reactive material is a sensor of the ambient, the consumed electrical energy being the sensing magnitude. Devices based on any of the electrochemical properties of conducting polymers must act simultaneously as sensors of the working conditions. Artificial muscles, as electrochemical actuators constituted by reactive materials, respond to the ambient conditions during actuation. In this way, they can be used as actuators, sensing the surrounding conditions during actuation. Actuating and sensing signals are simultaneously included by the same two connecting wires.

  4. Estimation of incremental reactivities for multiple day scenarios: an application to ethane and dimethyoxymethane

    Science.gov (United States)

    Stockwell, William R.; Geiger, Harald; Becker, Karl H.

    Single-day scenarios are used to calculate incremental reactivities by definition (Carter, J. Air Waste Management Assoc. 44 (1994) 881-899.) but even unreactive organic compounds may have a non-negligible effect on ozone concentrations if multiple-day scenarios are considered. The concentration of unreactive compounds and their products may build up over a multiple-day period and the oxidation products may be highly reactive or highly unreactive affecting the overall incremental reactivity of the organic compound. We have developed a method for calculating incremental reactivities for multiple days based on a standard scenario for polluted European conditions. This method was used to estimate maximum incremental reactivities (MIR) and maximum ozone incremental reactivities (MOIR) for ethane and dimethyoxymethane for scenarios ranging from 1 to 6 days. It was found that the incremental reactivities increased as the length of the simulation period increased. The MIR of ethane increased faster than the value for dimethyoxymethane as the scenarios became longer. The MOIRs of ethane and dimethyoxymethane increased but the change was more modest for scenarios longer than 3 days. MOIRs of both volatile organic compounds were equal within the uncertainties of their chemical mechanisms by the 5 day scenario. These results show that dimethyoxymethane has an ozone forming potential on a per mass basis that is only somewhat greater than ethane if multiple-day scenarios are considered.

  5. Nitrogen-rich heterocycles as reactivity retardants in shocked insensitive explosives.

    Science.gov (United States)

    Manaa, M Riad; Reed, Evan J; Fried, Laurence E; Goldman, Nir

    2009-04-22

    We report the first quantum-based multiscale simulations to study the reactivity of shocked perfect crystals of the insensitive energetic material triaminotrinitrobenzene (TATB). Tracking chemical transformations of TATB experiencing overdriven shock speeds of 9 km/s for up to 0.43 ns and 10 km/s for up to 0.2 ns reveal high concentrations of nitrogen-rich heterocyclic clusters. Further reactivity of TATB toward the final decomposition products of fluid N(2) and solid carbon is inhibited due to the formation of these heterocycles. Our results thus suggest a new mechanism for carbon-rich explosive materials that precedes the slow diffusion-limited process of forming the bulk solid from carbon clusters and provide fundamental insight at the atomistic level into the long reaction zone of shocked TATB.

  6. Flows and chemical reactions in homogeneous mixtures

    CERN Document Server

    Prud'homme, Roger

    2013-01-01

    Flows with chemical reactions can occur in various fields such as combustion, process engineering, aeronautics, the atmospheric environment and aquatics. The examples of application chosen in this book mainly concern homogeneous reactive mixtures that can occur in propellers within the fields of process engineering and combustion: - propagation of sound and monodimensional flows in nozzles, which may include disequilibria of the internal modes of the energy of molecules; - ideal chemical reactors, stabilization of their steady operation points in the homogeneous case of a perfect mixture and c

  7. Chemical Reactivity of Isoproturon, Diuron, Linuron, and Chlorotoluron Herbicides in Aqueous Phase: A Theoretical Quantum Study Employing Global and Local Reactivity Descriptors

    Directory of Open Access Journals (Sweden)

    Luis Humberto Mendoza-Huizar

    2015-01-01

    Full Text Available We have calculated global and local DFT reactivity descriptors for isoproturon, diuron, linuron, and chlorotoluron herbicides at the MP2/6-311++G(2d,2p level of theory. The results suggest that, in aqueous conditions, chlorotoluron, linuron, and diuron herbicides may be degraded by elimination of urea moiety through electrophilic attacks. On the other hand, electrophilic, nucleophilic, and free radical attacks on isoproturon may cause the elimination of isopropyl fragment.

  8. Structure and Reactivity of Zeolite- and Carbon-Supported Catalysts for the Oxidative Carbonylation of Alcohols

    OpenAIRE

    Briggs, Daniel Neal

    2010-01-01

    AbstractStructure and Reactivity of Zeolite- and Carbon-Supported Catalysts for the Oxidative Carbonylation of AlcoholsbyDaniel Neal BriggsDoctor of Philosophy in Chemical EngineeringUniversity of California, BerkeleyProfessor Alexis T. Bell, Chair The oxidative carbonylation of alcohols to produce dialkyl carbonates is a process that takes place commercially in a slurry of cuprous chloride in the appropriate alcohol. While this process is chemically efficient, it incurs costs in terms of ene...

  9. Ultrasound in chemical processes

    International Nuclear Information System (INIS)

    Baig, S.; Farooq, R.; Malik, A.H.

    2009-01-01

    The use of ultrasound to promote chemical reactions or sono chemistry is a field of chemistry which involves the process of acoustic cavitations i.e. the collapse of microscopic bubbles in liquid. There are two essential components for the application of sono chemistry, a liquid medium and a source of high-energy vibrations. The liquid medium is necessary because sono chemistry is driven by acoustic cavitations that can only occur in liquids. The source of the vibrational energy is the transducer. The chemical effects of ultrasound include the enhancement of reaction rates at ambient temperatures and striking advancements in stoichiometric and catalytic reactions In some cases, ultrasonic irradiation can increase reactivities by nearly million fold. The ultrasound has large number of applications not only in emending old chemical processes but also in developing new synthetic strategies. Ultrasound enhances all chemical and physical processes e.g., crystallization, vitamin synthesis, preparation of catalysts, dissolution of chemicals, organometallic reactions, electrochemical processes, etc. High-power ultrasonics is a new powerful technology that is not only safe and environmentally friendly in its application but is also efficient and economical. It can be applied to existing processes to eliminate the need for chemicals and/or heat application in a variety of industrial processes. (author)

  10. Simulating Chemical Kinetics Without Differential Equations: A Quantitative Theory Based on Chemical Pathways.

    Science.gov (United States)

    Bai, Shirong; Skodje, Rex T

    2017-08-17

    A new approach is presented for simulating the time-evolution of chemically reactive systems. This method provides an alternative to conventional modeling of mass-action kinetics that involves solving differential equations for the species concentrations. The method presented here avoids the need to solve the rate equations by switching to a representation based on chemical pathways. In the Sum Over Histories Representation (or SOHR) method, any time-dependent kinetic observable, such as concentration, is written as a linear combination of probabilities for chemical pathways leading to a desired outcome. In this work, an iterative method is introduced that allows the time-dependent pathway probabilities to be generated from a knowledge of the elementary rate coefficients, thus avoiding the pitfalls involved in solving the differential equations of kinetics. The method is successfully applied to the model Lotka-Volterra system and to a realistic H 2 combustion model.

  11. Reactive tunnel junctions in electrically driven plasmonic nanorod metamaterials

    Science.gov (United States)

    Wang, Pan; Krasavin, Alexey V.; Nasir, Mazhar E.; Dickson, Wayne; Zayats, Anatoly V.

    2018-02-01

    Non-equilibrium hot carriers formed near the interfaces of semiconductors or metals play a crucial role in chemical catalysis and optoelectronic processes. In addition to optical illumination, an efficient way to generate hot carriers is by excitation with tunnelling electrons. Here, we show that the generation of hot electrons makes the nanoscale tunnel junctions highly reactive and facilitates strongly confined chemical reactions that can, in turn, modulate the tunnelling processes. We designed a device containing an array of electrically driven plasmonic nanorods with up to 1011 tunnel junctions per square centimetre, which demonstrates hot-electron activation of oxidation and reduction reactions in the junctions, induced by the presence of O2 and H2 molecules, respectively. The kinetics of the reactions can be monitored in situ following the radiative decay of tunnelling-induced surface plasmons. This electrically driven plasmonic nanorod metamaterial platform can be useful for the development of nanoscale chemical and optoelectronic devices based on electron tunnelling.

  12. Large-Scale Reactive Atomistic Simulation of Shock-induced Initiation Processes in Energetic Materials

    Science.gov (United States)

    Thompson, Aidan

    2013-06-01

    Initiation in energetic materials is fundamentally dependent on the interaction between a host of complex chemical and mechanical processes, occurring on scales ranging from intramolecular vibrations through molecular crystal plasticity up to hydrodynamic phenomena at the mesoscale. A variety of methods (e.g. quantum electronic structure methods (QM), non-reactive classical molecular dynamics (MD), mesoscopic continuum mechanics) exist to study processes occurring on each of these scales in isolation, but cannot describe how these processes interact with each other. In contrast, the ReaxFF reactive force field, implemented in the LAMMPS parallel MD code, allows us to routinely perform multimillion-atom reactive MD simulations of shock-induced initiation in a variety of energetic materials. This is done either by explicitly driving a shock-wave through the structure (NEMD) or by imposing thermodynamic constraints on the collective dynamics of the simulation cell e.g. using the Multiscale Shock Technique (MSST). These MD simulations allow us to directly observe how energy is transferred from the shockwave into other processes, including intramolecular vibrational modes, plastic deformation of the crystal, and hydrodynamic jetting at interfaces. These processes in turn cause thermal excitation of chemical bonds leading to initial chemical reactions, and ultimately to exothermic formation of product species. Results will be presented on the application of this approach to several important energetic materials, including pentaerythritol tetranitrate (PETN) and ammonium nitrate/fuel oil (ANFO). In both cases, we validate the ReaxFF parameterizations against QM and experimental data. For PETN, we observe initiation occurring via different chemical pathways, depending on the shock direction. For PETN containing spherical voids, we observe enhanced sensitivity due to jetting, void collapse, and hotspot formation, with sensitivity increasing with void size. For ANFO, we

  13. Journal of Chemical Sciences | Indian Academy of Sciences

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 125; Issue 6. Reactivity of allenylphosphonates and allenylphosphine oxides toward 9-chloroacridines and acridone- A facile route to new -substituted acridones. A Leela Siva Kumari Venu Srinivas K C Kumara Swamy. Regular Articles Volume 125 Issue 6 ...

  14. The reactivity of ion-implanted SiC

    International Nuclear Information System (INIS)

    McHargue, C.J.; Lewis, M.B.; Williams, J.M.; Appleton, B.R.

    1985-01-01

    Implantation of chromium into single crystal or polycrystalline α-SiC produces a surface amorphous layer for displacement damage greater than about 0.2 displacements per atom at room temperature. The enhanced chemical reactivity of such specimens was studied by two methods: chemical etching rate and oxidation rate. The chemical etching rates in a saturated solution of 50% K 3 Fe(CN) 6 plus 50% KOH were measured. The etching rate for the amorphous layer was 2.4-3.7 times that of the polycrystalline samples and 3.0-4.1 times that of the single-crystal samples. Polycrystalline specimens were exposed to flowing oxygen for 1 h at 1300 0 C. Rutherford backscattering and the nuclear reaction 16 O(d,p) 17 O* were used to determine the amount of oxygen on the surface. The amount of oxygen (and the thickness of oxide) over the amorphous region was 1.67 times that over the crystalline region. The relative thicknesses of the oxide on the amorphous and crystalline regions were confirmed by measuring the sputtering time required to remove the oxygen signal in an Auger spectrometer. (Auth.)

  15. The study of mechanical properties and reactive stresses in the i-Ni-Nb shape memory alloys

    International Nuclear Information System (INIS)

    Popov, N.N.; Sysoeva, T.I.; Lar'kin, V.F.; Vedernikova, I.I.; Prokoshkin, S.D.

    2007-01-01

    One investigated into the effect of the induced deformation value, rate and temperature, of the thermal treatment procedure and of the chemical composition on the mechanical properties and the development of the reactive stresses in Ti-Ni-Nb system shape memory alloys. One showed the effect of the material composition and of the deformation temperature on the mechanical features of the investigated alloys. One determined the temperature and deformation conditions ensuring the maximum level of the reactive stresses in the alloys. One revealed the dependence of the maximum reactive stress value on the austenite mechanical features, namely, on its yield limit. One chose Ti-Ni-Nb alloy compositions applicable in the pipeline thermomechanical connections [ru

  16. Abiotic/biotic coupling in the rhizosphere: a reactive transport modeling analysis

    Science.gov (United States)

    Lawrence, Corey R.; Steefel, Carl; Maher, Kate

    2014-01-01

    A new generation of models is needed to adequately simulate patterns of soil biogeochemical cycling in response changing global environmental drivers. For example, predicting the influence of climate change on soil organic matter storage and stability requires models capable of addressing complex biotic/abiotic interactions of rhizosphere and weathering processes. Reactive transport modeling provides a powerful framework simulating these interactions and the resulting influence on soil physical and chemical characteristics. Incorporation of organic reactions in an existing reactive transport model framework has yielded novel insights into soil weathering and development but much more work is required to adequately capture root and microbial dynamics in the rhizosphere. This endeavor provides many advantages over traditional soil biogeochemical models but also many challenges.

  17. Chemical Passivation of Li(exp +)-Conducting Solid Electrolytes

    Science.gov (United States)

    West, William; Whitacre, Jay; Lim, James

    2008-01-01

    Plates of a solid electrolyte that exhibits high conductivity for positive lithium ions can now be passivated to prevent them from reacting with metallic lithium. Such passivation could enable the construction and operation of high-performance, long-life lithium-based rechargeable electrochemical cells containing metallic lithium anodes. The advantage of this approach, in comparison with a possible alternative approach utilizing lithium-ion graphitic anodes, is that metallic lithium anodes could afford significantly greater energy-storage densities. A major impediment to the development of such cells has been the fact that the available solid electrolytes having the requisite high Li(exp +)-ion conductivity are too highly chemically reactive with metallic lithium to be useful, while those solid electrolytes that do not react excessively with metallic lithium have conductivities too low to be useful. The present passivation method exploits the best features of both extremes of the solid-electrolyte spectrum. The basic idea is to coat a higher-conductivity, higher-reactivity solid electrolyte with a lower-conductivity, lower-reactivity solid electrolyte. One can then safely deposit metallic lithium in contact with the lower-reactivity solid electrolyte without incurring the undesired chemical reactions. The thickness of the lower-reactivity electrolyte must be great enough to afford the desired passivation but not so great as to contribute excessively to the electrical resistance of the cell. The feasibility of this method was demonstrated in experiments on plates of a commercial high-performance solid Li(exp +)- conducting electrolyte. Lithium phosphorous oxynitride (LiPON) was the solid electrolyte used for passivation. LiPON-coated solid-electrolyte plates were found to support electrochemical plating and stripping of Li metal. The electrical resistance contributed by the LiPON layers were found to be small relative to overall cell impedances.

  18. The mystery of gold's chemical activity: local bonding, morphology and reactivity of atomic oxygen.

    Science.gov (United States)

    Baker, Thomas A; Liu, Xiaoying; Friend, Cynthia M

    2011-01-07

    Recently, gold has been intensely studied as a catalyst for key synthetic reactions. Gold is an attractive catalyst because, surprisingly, it is highly active and very selective for partial oxidation processes suggesting promise for energy-efficient "green" chemistry. The underlying origin of the high activity of Au is a controversial subject since metallic gold is commonly thought to be inert. Herein, we establish that one origin of the high activity for gold catalysis is the extremely reactive nature of atomic oxygen bound in 3-fold coordination sites on metallic gold. This is the predominant form of O at low concentrations on the surface, which is a strong indication that it is most relevant to catalytic conditions. Atomic oxygen bound to metallic Au in 3-fold sites has high activity for CO oxidation, oxidation of olefins, and oxidative transformations of alcohols and amines. Among the factors identified as important in Au-O interaction are the morphology of the surface, the local binding site of oxygen, and the degree of order of the oxygen overlayer. In this Perspective, we present an overview of both theory and experiments that identify the reactive forms of O and their associated charge density distributions and bond strengths. We also analyze and model the release of Au atoms induced by O binding to the surface. This rough surface also has the potential for O(2) dissociation, which is a critical step if Au is to be activated catalytically. We further show the strong parallels between product distributions and reactivity for O-covered Au at low pressure (ultrahigh vacuum) and for nanoporous Au catalysts operating at atmospheric pressure as evidence that atomic O is the active species under working catalytic conditions when metallic Au is present. We briefly discuss the possible contributions of oxidants that may contain intact O-O bonds and of the Au-metal oxide support interface in Au catalysis. Finally, the challenges and future directions for fully

  19. Host-guest complex of N-(2-chloroethyl), N-nitroso, N‧, N‧ -dicyclohexylsulfamid with β-cyclodextrin: Fluorescence, QTAIM analysis and structure-chemical reactivity

    Science.gov (United States)

    Bensouilah, Nadjia; Fisli, Hassina; Bensouilah, Hamza; Zaater, Sihem; Abdaoui, Mohamed; Boutemeur-Kheddis, Baya

    2017-10-01

    In this work, the inclusion complex of DCY/CENS: N-(2-chloroethyl), N-nitroso, N‧, N‧-dicyclohexylsulfamid and β-cyclodextrin (β-CD) is investigated using the fluorescence spectroscopy, PM3, ONIOM2 and DFT methods. The experimental part reveals that DCY/CENS forms a 1:1 stoichiometric ratio inclusion complex with β-CD. The constant of stability is evaluated using the Benesi-Hildebrand equation. The results of the theoretical optimization showed that the lipophilic fraction of molecule (cyclohexyl group) is inside of β-CD. Accordingly, the Nitroso-Chloroethyl moiety is situated outside the cavity of the macromolecule host. The favorable structure of the optimized complex indicates the existence of weak intermolecular hydrogen bonds and the most important van der Waals (vdW) interactions which are studied on the basis of Natural Bonding Orbital (NBO) analysis. The NBO is employed to compute the electronic donor-acceptor exchanges between drug and β-CD. Furthermore, a detailed topological charge density analysis based on the quantum theory of atoms in molecules (QTAIM), has been accomplished on the most favorable complex using B3LYP/6-31G(d) method. The presence of stabilizing intermolecular hydrogen bonds and van der Waals interactions in the most favorable complex is predicted. Also, the energies of these interactions are estimated with Espinosa's formula. The findings of this investigation reveal that the correlation between the structural parameters and the electronic density is good. Finally, and based on DFT calculations, the reactivity of the interesting molecule in free state was studied and compared with that in the complexed state using chemical potential, global hardness, global softness, electronegativity, electrophilicity and local reactivity descriptors.

  20. Reactivity indexes for different geometries of palladium leads

    Energy Technology Data Exchange (ETDEWEB)

    Gomez-Carrillo, S C; Bolcatto, P G [Departamento de Fisica, Facultad de Ingenieria Quimica, Universidad Nacional de Litoral, Santiago del Estero 2829 S3000AOM Santa Fe Argentina (Argentina); Ortega, J, E-mail: scgomez@fiq.unl.edu.a [Departamento de Fisica Teorica de la Materia Condensada, Universidad Autonoma de Madrid (Spain)

    2009-05-01

    Electronic transport through metallic break junctions or molecules is clearly dependent not only on the electronic structure of the central nanodevice connecting the leads, but also the shape and crystalline orientation of the contacts which can define the possible conduction channels. In this work we examine different geometries of contacts of palladium characterizing them through global and local reactivity indexes as electrophilicity, chemical hardness and Fukui functions. In molecules, these indicators are essentially defined by the energies of the frontier molecular orbitals and in solids they are related with the local and partial density of states. We use for this purpose an ab-initio based code (FIREBALL), applied to plane contacts with (001) fcc faces and also pyramidal tips grown following a (001) and (111) packaging. The results allow us to have an insight about the chemical features of this type of nanojunctions.

  1. How a gold substrate can increase the reactivity of a Pt overlayer

    DEFF Research Database (Denmark)

    Pedersen, Morten Ø.; Helveg, Stig; Ruban, Andrei

    1999-01-01

    The growth and chemical reactivity of Pt on Au(111) have been studied using scanning tunneling microscopy (STM) and temperature programmed desorption (TPD). Deposition of Pt at coverages from 0.02 ML up to 2.5 ML on Au(111) at room temperature initially leads to the formation of a surface alloy......, in which 3% of the Au atoms are replaced by Pt. Subsequent Pt evaporation leads to island growth with a mixed Pt-Au island composition. The reactivity of the Pt/Au system is studied using CO as a probe molecule. We show that a stronger bonding of CO to the first layer of Pt on Au(111) exists compared...... with the binding of CO on clean Pt. The Au substrate therefore very surprisingly increases the Pt overlayer reactivity. The results can be understood in a simple model, in which the change in the CO binding energy is directly proportional to the shift of the d-band center of the metal overlayer. According...

  2. Synthesis of gallium nitride and related oxides via ammonobasic reactive sublimation (ARS)

    Energy Technology Data Exchange (ETDEWEB)

    Hernández-Hernández, Luis Alberto; Aguilar-Hernández, Jorge R.; Mejía-García, Concepción; Cruz-Gandarilla, Francisco; Contreras-Puente, Gerardo [Escuela Superior de Física y Matemáticas, Instituto Politécnico Nacional, Ciudad de México (Mexico); Moure-Flores, Francisco de [Facultad de Química, Materiales-Energía, Universidad Autónoma de Querétaro (Mexico); Melo-Pereira, Osvaldo de, E-mail: schwarzerengelxv@hotmail.com [Facultad de Física, Universidad de La Habana, La Habana (Cuba)

    2017-11-15

    Ammonobasic reactive sublimation (ARS) is proposed as a novel method to synthesize GaN and related oxides. Results indicate that GaN growth occurs by a nitriding process of Ga and related oxides, establishing a direct dependence on NH{sub 4} OH amount added as a primary chemical reactive. The samples were grown on p-type Si (111) substrates inside a tube furnace, employing GaN powder and NH{sub 4} OH. The characterizations of the samples were carried out by XRD, SEM, EDS and PL techniques, revealing the influence of NH{sub 4} OH on the improvement of GaN synthesis and the enhancement of its optical and structural properties. (author)

  3. RMP Guidance for Chemical Distributors - Appendix D: OSHA Guidance on PSM

    Science.gov (United States)

    Guidance on the Process Safety Management standard says information (including MSDS) about chemicals, including process intermediates, must enable accurate assessment of fire/explosion characteristics, reactivity hazards, and corrosing/erosion effects.

  4. Method of controlling reactivity

    International Nuclear Information System (INIS)

    Tochihara, Hiroshi.

    1982-01-01

    Purpose: To improve the reactivity controlling characteristics by artificially controlling the leakage of neutron from a reactor and providing a controller for controlling the reactivity. Method: A reactor core is divided into several water gaps to increase the leakage of neutron, its reactivity is reduced, a gas-filled control rod or a fuel assembly is inserted into the gap as required, the entire core is coupled in a system to reduce the leakage of the neutron, and the reactivity is increased. The reactor shutdown is conducted by the conventional control rod, and to maintain critical state, boron density varying system is used together. Futher, a control rod drive is used with that similar to the conventional one, thereby enabling fast reactivity variation, and the positive reactivity can be obtained by the insertion, thereby improving the reactivity controlling characteristics. (Yoshihara, H.)

  5. Dissecting molecular descriptors into atomic contributions in density functional reactivity theory

    International Nuclear Information System (INIS)

    Rong, Chunying; Lu, Tian; Liu, Shubin

    2014-01-01

    Density functional reactivity theory (DFRT) employs the electron density of a molecule and its related quantities such as gradient and Laplacian to describe its structure and reactivity properties. Proper descriptions at both molecular (global) and atomic (local) levels are equally important and illuminating. In this work, we make use of Bader's zero-flux partition scheme and consider atomic contributions for a few global reactivity descriptors in DFRT, including the density-based quantification of steric effect and related indices. Earlier, we proved that these quantities are intrinsically correlated for atomic and molecular systems [S. B. Liu, J. Chem. Phys. 126, 191107 (2007); ibid. 126, 244103 (2007)]. In this work, a new basin-based integration algorithm has been implemented, whose reliability and effectiveness have been extensively examined. We also investigated a list of simple hydrocarbon systems and different scenarios of bonding processes, including stretching, bending, and rotating. Interesting changing patterns for the atomic and molecular values of these quantities have been revealed for different systems. This work not only confirms the strong correlation between these global reactivity descriptors for molecular systems, as theoretically proven earlier by us, it also provides new and unexpected changing patterns for their atomic values, which can be employed to understand the origin and nature of chemical phenomena

  6. Dissecting molecular descriptors into atomic contributions in density functional reactivity theory

    Energy Technology Data Exchange (ETDEWEB)

    Rong, Chunying [Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research (Ministry of Education of China) and Key Laboratory of Resource Fine-Processing and Advanced Materials of Hunan Province, College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha, Hunan 410081 (China); Lu, Tian [School of Chemical and Biological Engineering, University of Science and Technology Beijing, Beijing (China); Liu, Shubin, E-mail: shubin@email.unc.edu [Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research (Ministry of Education of China) and Key Laboratory of Resource Fine-Processing and Advanced Materials of Hunan Province, College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha, Hunan 410081 (China); Research Computing Center, University of North Carolina, Chapel Hill, North Carolina 27599-3420 (United States)

    2014-01-14

    Density functional reactivity theory (DFRT) employs the electron density of a molecule and its related quantities such as gradient and Laplacian to describe its structure and reactivity properties. Proper descriptions at both molecular (global) and atomic (local) levels are equally important and illuminating. In this work, we make use of Bader's zero-flux partition scheme and consider atomic contributions for a few global reactivity descriptors in DFRT, including the density-based quantification of steric effect and related indices. Earlier, we proved that these quantities are intrinsically correlated for atomic and molecular systems [S. B. Liu, J. Chem. Phys. 126, 191107 (2007); ibid. 126, 244103 (2007)]. In this work, a new basin-based integration algorithm has been implemented, whose reliability and effectiveness have been extensively examined. We also investigated a list of simple hydrocarbon systems and different scenarios of bonding processes, including stretching, bending, and rotating. Interesting changing patterns for the atomic and molecular values of these quantities have been revealed for different systems. This work not only confirms the strong correlation between these global reactivity descriptors for molecular systems, as theoretically proven earlier by us, it also provides new and unexpected changing patterns for their atomic values, which can be employed to understand the origin and nature of chemical phenomena.

  7. Reactive Arthritis

    Directory of Open Access Journals (Sweden)

    Eren Erken

    2013-06-01

    Full Text Available Reactive arthritis is an acute, sterile, non-suppurative and inflammatory arthropaty which has occured as a result of an infectious processes, mostly after gastrointestinal and genitourinary tract infections. Reiter syndrome is a frequent type of reactive arthritis. Both reactive arthritis and Reiter syndrome belong to the group of seronegative spondyloarthropathies, associated with HLA-B27 positivity and characterized by ongoing inflammation after an infectious episode. The classical triad of Reiter syndrome is defined as arthritis, conjuctivitis and urethritis and is seen only in one third of patients with Reiter syndrome. Recently, seronegative asymmetric arthritis and typical extraarticular involvement are thought to be adequate for the diagnosis. However, there is no established criteria for the diagnosis of reactive arthritis and the number of randomized and controlled studies about the therapy is not enough. [Archives Medical Review Journal 2013; 22(3.000: 283-299

  8. Quasi-equilibria and plasma chemical similarity in non-isothermal reactive plasmas

    International Nuclear Information System (INIS)

    Miethke, F.; Rutscher, A.; Wagner, H.E.

    2000-01-01

    With regard to the output of stable products the mode of operation of non-isothermal plasma chemical reactors shows physical and chemical well defined states, which represent limiting cases and may be interpreted as quasi-equilibrium states. The occurrence and the characteristics of these states, meanwhile more than once observed and described, are demonstrated by an instructive model reaction. Within the frame of the so-called Macroscopic Kinetics a central parameter is dominating the reactor operation. This result may be generalized and is linked up to the application of similarity principles for the reactor operation. After the general formulation of such principles, starting from the balance equations of particles and energy, a dimensionless similarity parameter is formulated, characterizing the composition of the effluent gas of the reactor. The applicability of this parameter is demonstrated by experimental examples. (Authors)

  9. Passivation of bimetallic catalysts used in water treatment: prevention and reactivation.

    Science.gov (United States)

    Chen, Jianming; Gillham, Robert W; Gui, Lai

    2013-01-01

    With respect to degradation rates and the range in contaminants treated, bimetals such as Ni-Fe or Pd-Fe generally outperform unamended granular iron. However, the catalytic enhancement is generally short-lived, lasting from a few days to months. To take advantage of the significant benefits of bimetals, this study aims at developing an effective method for the rejuvenation of passivated bimetals and alternatively, the prevention of rapid reactivity loss of bimetals. Because the most likely cause of Ni-Fe and Pd-Fe passivation is the deposition of iron oxide films over the catalyst sites, it is hypothesized that removal of the iron oxide films will restore the lost reactivity or avoiding the deposition of iron oxide films will prevent passivation. Two organic ligands (ethylenediaminetetraacetic acid (EDTA), and [s,s]-ethylenediaminedisuccinate acid ([s,s]-EDDS)) and two acids (citric acid and sulphuric acid) were tested as possible chemical reagents for both passivation rejuvenation and prevention. Trichloroethene (TCE) and Ni-Fe were chosen as probes for chlorinated solvents and bimetals respectively. The test was carried out using small glass columns packed with Ni-Fe. TCE solution containing a single reagent at various concentrations was pumped through the Ni-Fe columns with a residence time in the Ni-Fe of about 6.6 min. TCE concentrations in the influent and effluent were measured to evaluate the performance of each chemical reagent. The results show that (i) for passivated Ni-Fe, flushing with a low concentration of acid or ligand solution without mechanical mixing can fully restore the lost reactivity; and (ii) for passivation prevention, adding a small amount of a ligand or an acid to the feed solution can successfully prevent or at least substantially reduce Ni-Fe passivation. All four chemicals tested are effective in both rejuvenation and prevention, but sulphuric acid and citric acid are considered to be the most practical reagents due to their

  10. Quantum chemical study of the structure, spectroscopy and reactivity of NO+.(H2O)n=1-5 clusters

    Science.gov (United States)

    Linton, Kirsty A.; Wright, Timothy G.; Besley, Nicholas A.

    2018-03-01

    Quantum chemical methods including Møller-Plesset perturbation (MP2) theory and density functional theory (DFT) have been used to study the structure, spectroscopy and reactivity of NO+.(H2O)n=1-5 clusters. MP2/6-311++G** calculations are shown to describe the structure and spectroscopy of the clusters well. DFT calculations with exchange-correlation functionals with a low fraction of Hartree-Fock exchange give a binding energy of NO+.(H2O) that is too high and incorrectly predict the lowest energy structure of NO+.(H2O)2, and this error may be associated with a delocalization of charge onto the water molecule directly binding to NO+. Ab initio molecular dynamics (AIMD) simulations were performed to study the NO+.(H2O)5 H+.(H2O)4 + HONO reaction to investigate the formation of HONO from NO+.(H2O)5. Whether an intracluster reaction to form HONO is observed depends on the level of electronic structure theory used. Of note is that methods that accurately describe the relative energies of the product and reactant clusters did not show reactions on the timescales studied. This suggests that in the upper atmosphere the reaction may occur owing to the energy present in the NO+.(H2O)5 complex following its formation. This article is part of the theme issue `Modern theoretical chemistry'.

  11. Mineralogy controls on reactive transport of Marcellus Shale waters.

    Science.gov (United States)

    Cai, Zhang; Wen, Hang; Komarneni, Sridhar; Li, Li

    2018-07-15

    Produced or flowback waters from Marcellus Shale gas extraction (MSWs) typically are highly saline and contain chemicals including trace metals, which pose significant concerns on water quality. The natural attenuation of MSW chemicals in groundwater is poorly understood due to the complex interactions between aquifer minerals and MSWs, limiting our capabilities to monitor and predict. Here we combine flow-through experiments and process-based reactive transport modeling to understand mechanisms and quantify the retention of MSW chemicals in a quartz (Qtz) column, a calcite-rich (Cal) column, and a clay-rich (Vrm, vermiculite) column. These columns were used to represent sand, carbonate, and clay-rich aquifers. Results show that the types and extent of water-rock interactions differ significantly across columns. Although it is generally known that clay-rich media retard chemicals and that quartz media minimize water-rock interactions, results here have revealed insights that differ from previous thoughts. We found that the reaction mechanisms are much more complex than merely sorption and mineral precipitation. In clay rich media, trace metals participate in both ion exchange and mineral precipitation. In fact, the majority of metals (~50-90%) is retained in the solid via mineral precipitation, which is surprising because we typically expect the dominance of sorption in clay-rich aquifers. In the Cal column, trace metals are retained not only through precipitation but also solid solution partitioning, leading to a total of 75-99% retention. Even in the Qtz column, trace metals are retained at unexpectedly high percentages (~20-70%) due to precipitation. The reactive transport model developed here quantitatively differentiates the relative importance of individual processes, and bridges a limited number of experiments to a wide range of natural conditions. This is particularly useful where relatively limited knowledge and data prevent the prediction of complex rock

  12. Reactive Strength Index: A Poor Indicator of Reactive Strength?

    Science.gov (United States)

    Healy, Robin; Kenny, Ian; Harrison, Drew

    2017-11-28

    The primary aim was to assess the relationships between reactive strength measures and associated kinematic and kinetic performance variables achieved during drop jumps. A secondary aim was to highlight issues with the use of reactive strength measures as performance indicators. Twenty eight national and international level sprinters, consisting of fourteen men and women, participated in this cross-sectional analysis. Athletes performed drop jumps from a 0.3 m box onto a force platform with dependent variables contact time (CT), landing time (TLand), push-off time (TPush), flight time (FT), jump height (JH), reactive strength index (RSI, calculated as JH / CT), reactive strength ratio (RSR, calculated as FT / CT) and vertical leg spring stiffness (Kvert) recorded. Pearson's correlation test found very high to near perfect relationships between RSI and RSR (r = 0.91 to 0.97), with mixed relationships found between RSI, RSR and the key performance variables, (Men: r = -0.86 to -0.71 between RSI/RSR and CT, r = 0.80 to 0.92 between RSI/RSR and JH; Women: r = -0.85 to -0.56 between RSR and CT, r = 0.71 between RSI and JH). This study demonstrates that the method of assessing reactive strength (RSI versus RSR) may be influenced by the performance strategies adopted i.e. whether an athlete achieves their best reactive strength scores via low CTs, high JHs or a combination. Coaches are advised to limit the variability in performance strategies by implementing upper and / or lower CT thresholds to accurately compare performances between individuals.

  13. A Chemo-Mechanical Model of Diffusion in Reactive Systems

    Directory of Open Access Journals (Sweden)

    Kerstin Weinberg

    2018-02-01

    Full Text Available The functional properties of multi-component materials are often determined by a rearrangement of their different phases and by chemical reactions of their components. In this contribution, a material model is presented which enables computational simulations and structural optimization of solid multi-component systems. Typical Systems of this kind are anodes in batteries, reactive polymer blends and propellants. The physical processes which are assumed to contribute to the microstructural evolution are: (i particle exchange and mechanical deformation; (ii spinodal decomposition and phase coarsening; (iii chemical reactions between the components; and (iv energetic forces associated with the elastic field of the solid. To illustrate the capability of the deduced coupled field model, three-dimensional Non-Uniform Rational Basis Spline (NURBS based finite element simulations of such multi-component structures are presented.

  14. Energy transfer in reactive and non-reactive H2 + OH collisions

    International Nuclear Information System (INIS)

    Rashed, O.; Brown, N.J.

    1985-04-01

    We have used the methods of quasi-classical dynamics to compute energy transfer properties of non-reactive and reactive H 2 + OH collisions. Energy transfer has been investigated as function of translational temperature, reagent rotational energy, and reagent vibrational energy. The energy transfer mechanism is complex with ten types of energy transfer possible, and evidence was found for all types. There is much more exchange between the translational degree of freedom and the H 2 vibrational degree of freedom than there is between translation and OH vibration. Translational energy is transferred to the rotational degrees of freedom of each molecule. There is a greater propensity for the transfer of translation to OH rotation than H 2 rotation. In reactive collisions, increases in reagent translational temperature predominantly appear as vibrational energy in the water molecule. Energy transfer in non-reactive and reactive collisions does not depend strongly on the initial angular momentum in either molecule. In non-reactive collisions, vibrational energy is transferred to translation, to the rotational degree of freedom of the same molecule, and to the rotational and vibrational degrees of freedom of the other molecule. In reactive collisions, the major effect of increasing the vibrational energy in reagent molecules is that, on the average, the vibrational energy of the reagents appears as product vibrational energy. 18 refs., 16 figs., 6 tabs

  15. Toxicological and pathophysiological roles of reactive oxygen and nitrogen species

    International Nuclear Information System (INIS)

    Roberts, Ruth A.; Smith, Robert A.; Safe, Stephen; Szabo, Csaba; Tjalkens, Ronald B.; Robertson, Fredika M.

    2010-01-01

    'Oxidative and Nitrative Stress in Toxicology and Disease' was the subject of a symposium held at the EUROTOX meeting in Dresden 15th September 2009. Reactive oxygen (ROS) and reactive nitrogen species (RNS) produced during tissue pathogenesis and in response to viral or chemical toxicants, induce a complex series of downstream adaptive and reparative events driven by the associated oxidative and nitrative stress. As highlighted by all the speakers, ROS and RNS can promote diverse biological responses associated with a spectrum of disorders including neurodegenerative/neuropsychiatric and cardiovascular diseases. Similar pathways are implicated during the process of liver and skin carcinogenesis. Mechanistically, reactive oxygen and nitrogen species drive sustained cell proliferation, cell death including both apoptosis and necrosis, formation of nuclear and mitochondrial DNA mutations, and in some cases stimulation of a pro-angiogenic environment. Here we illustrate the pivotal role played by oxidative and nitrative stress in cell death, inflammation and pain and its consequences for toxicology and disease pathogenesis. Examples are presented from five different perspectives ranging from in vitro model systems through to in vivo animal model systems and clinical outcomes.

  16. Defect-engineered graphene chemical sensors with ultrahigh sensitivity.

    Science.gov (United States)

    Lee, Geonyeop; Yang, Gwangseok; Cho, Ara; Han, Jeong Woo; Kim, Jihyun

    2016-05-25

    We report defect-engineered graphene chemical sensors with ultrahigh sensitivity (e.g., 33% improvement in NO2 sensing and 614% improvement in NH3 sensing). A conventional reactive ion etching system was used to introduce the defects in a controlled manner. The sensitivity of graphene-based chemical sensors increased with increasing defect density until the vacancy-dominant region was reached. In addition, the mechanism of gas sensing was systematically investigated via experiments and density functional theory calculations, which indicated that the vacancy defect is a major contributing factor to the enhanced sensitivity. This study revealed that defect engineering in graphene has significant potential for fabricating ultra-sensitive graphene chemical sensors.

  17. A reactive distillation process for the treatment of LiCl-KCl eutectic waste salt containing rare earth chlorides

    Energy Technology Data Exchange (ETDEWEB)

    Eun, H.C., E-mail: ehc2004@kaeri.re.kr; Choi, J.H.; Kim, N.Y.; Lee, T.K.; Han, S.Y.; Lee, K.R.; Park, H.S.; Ahn, D.H.

    2016-11-15

    The pyrochemical process, which recovers useful resources (U/TRU metals) from used nuclear fuel using an electrochemical method, generates LiCl-KCl eutectic waste salt containing radioactive rare earth chlorides (RECl{sub 3}). It is necessary to develop a simple process for the treatment of LiCl-KCl eutectic waste salt in a hot-cell facility. For this reason, a reactive distillation process using a chemical agent was achieved as a method to separate rare earths from the LiCl-KCl waste salt. Before conducting the reactive distillation, thermodynamic equilibrium behaviors of the reactions between rare earth (Nd, La, Ce, Pr) chlorides and the chemical agent (K{sub 2}CO{sub 3}) were predicted using software. The addition of the chemical agent was determined to separate the rare earth chlorides into an oxide form using these equilibrium results. In the reactive distillation test, the rare earth chlorides in LiCl-KCl eutectic salt were decontaminated at a decontamination factor (DF) of more than 5000, and were mainly converted into oxide (Nd{sub 2}O{sub 3}, CeO{sub 2}, La{sub 2}O{sub 3}, Pr{sub 2}O{sub 3}) or oxychloride (LaOCl, PrOCl) forms. The LiCl-KCl was purified into a form with a very low concentration (<1 ppm) for the rare earth chlorides.

  18. A Reactive Transport Model for Marcellus Shale Weathering

    Science.gov (United States)

    Li, L.; Heidari, P.; Jin, L.; Williams, J.; Brantley, S.

    2017-12-01

    factors affecting chemical weathering of the Marcellus shale in the shallow subsurface. This study documents the utility of reactive transport modeling for complex subsurface processes. Such modelling could be extended to understand interactions between injected fluids and Marcellus shale gas reservoirs at higher temperature and pressure.

  19. Feasibility of Batch Reactive Distillation with Equilibrium-Limited Consecutive Reactions in Rectifier, Stripper, or Middle-Vessel Column

    Directory of Open Access Journals (Sweden)

    T. Lukács

    2011-01-01

    Full Text Available A general overall feasibility methodology of batch reactive distillation of multireaction systems is developed to study all the possible configurations of batch reactive distillation. The general model equations are derived for multireaction system with any number of chemical equilibrium-limited reactions and for any number of components. The present methodology is demonstrated with the detailed study of the transesterification of dimethyl carbonate in two reversible cascade reactions in batch reactive distillation process. Pure methanol is produced as distillate, and pure diethyl carbonate is produced at the bottom simultaneously in middle-vessel column; in each section, continuous feeding of ethanol is necessary. The results of feasibility study are successfully validated by rigorous simulations.

  20. Chemical Changes in Nonthermal Plasma-Treated N-Acetylcysteine (NAC) Solution and Their Contribution to Bacterial Inactivation.

    Science.gov (United States)

    Ercan, Utku K; Smith, Josh; Ji, Hai-Feng; Brooks, Ari D; Joshi, Suresh G

    2016-02-02

    In continuation of our previous reports on the broad-spectrum antimicrobial activity of atmospheric non-thermal dielectric barrier discharge (DBD) plasma treated N-Acetylcysteine (NAC) solution against planktonic and biofilm forms of different multidrug resistant microorganisms, we present here the chemical changes that mediate inactivation of Escherichia coli. In this study, the mechanism and products of the chemical reactions in plasma-treated NAC solution are shown. UV-visible spectrometry, FT-IR, NMR, and colorimetric assays were utilized for chemical characterization of plasma treated NAC solution. The characterization results were correlated with the antimicrobial assays using determined chemical species in solution in order to confirm the major species that are responsible for antimicrobial inactivation. Our results have revealed that plasma treatment of NAC solution creates predominantly reactive nitrogen species versus reactive oxygen species, and the generated peroxynitrite is responsible for significant bacterial inactivation.

  1. Modeling variably saturated multispecies reactive groundwater solute transport with MODFLOW-UZF and RT3D

    Science.gov (United States)

    Bailey, Ryan T.; Morway, Eric D.; Niswonger, Richard G.; Gates, Timothy K.

    2013-01-01

    A numerical model was developed that is capable of simulating multispecies reactive solute transport in variably saturated porous media. This model consists of a modified version of the reactive transport model RT3D (Reactive Transport in 3 Dimensions) that is linked to the Unsaturated-Zone Flow (UZF1) package and MODFLOW. Referred to as UZF-RT3D, the model is tested against published analytical benchmarks as well as other published contaminant transport models, including HYDRUS-1D, VS2DT, and SUTRA, and the coupled flow and transport modeling system of CATHY and TRAN3D. Comparisons in one-dimensional, two-dimensional, and three-dimensional variably saturated systems are explored. While several test cases are included to verify the correct implementation of variably saturated transport in UZF-RT3D, other cases are included to demonstrate the usefulness of the code in terms of model run-time and handling the reaction kinetics of multiple interacting species in variably saturated subsurface systems. As UZF1 relies on a kinematic-wave approximation for unsaturated flow that neglects the diffusive terms in Richards equation, UZF-RT3D can be used for large-scale aquifer systems for which the UZF1 formulation is reasonable, that is, capillary-pressure gradients can be neglected and soil parameters can be treated as homogeneous. Decreased model run-time and the ability to include site-specific chemical species and chemical reactions make UZF-RT3D an attractive model for efficient simulation of multispecies reactive transport in variably saturated large-scale subsurface systems.

  2. Relationship between structure and reactivity in AOT inverse micelles

    International Nuclear Information System (INIS)

    Petit, Christophe

    1988-01-01

    As inverse micelles can be considered as chemical micro-reactors, the objective of this research thesis is to show that reaction rates can be modified, either by varying the size of micro-reactors, or by modifying the location of one of the reactants. After a brief overview of noticeable results obtained on AOT inverse micelles about the structure and reactivity, the author reports the study of structural modifications induced by an addition of small molecules or proteins. Two complementary models are proposed on this purpose: a geometrical model which reports the medium microscopic evolution and a kinetic model which could report the system microscopic evolution as well reactivity changes with respect to probe location. The next part reports the study of in situ synthesis of semi-conductor particles in AOT inverse micelles. The author then reports that a surprising aspect of macromolecule solubilization has been noticed: the solubilization of a polypeptide, gelatine, allows the whole system to be gelled whereas gelatine is essentially polar [fr

  3. Revisiting the definition of the electronic chemical potential, chemical hardness, and softness at finite temperatures

    International Nuclear Information System (INIS)

    Franco-Pérez, Marco; Gázquez, José L.; Ayers, Paul W.; Vela, Alberto

    2015-01-01

    We extend the definition of the electronic chemical potential (μ e ) and chemical hardness (η e ) to finite temperatures by considering a reactive chemical species as a true open system to the exchange of electrons, working exclusively within the framework of the grand canonical ensemble. As in the zero temperature derivation of these descriptors, the response of a chemical reagent to electron-transfer is determined by the response of the (average) electronic energy of the system, and not by intrinsic thermodynamic properties like the chemical potential of the electron-reservoir which is, in general, different from the electronic chemical potential, μ e . Although the dependence of the electronic energy on electron number qualitatively resembles the piecewise-continuous straight-line profile for low electronic temperatures (up to ca. 5000 K), the introduction of the temperature as a free variable smoothens this profile, so that derivatives (of all orders) of the average electronic energy with respect to the average electron number exist and can be evaluated analytically. Assuming a three-state ensemble, well-known results for the electronic chemical potential at negative (−I), positive (−A), and zero values of the fractional charge (−(I + A)/2) are recovered. Similarly, in the zero temperature limit, the chemical hardness is formally expressed as a Dirac delta function in the particle number and satisfies the well-known reciprocity relation with the global softness

  4. Photoluminescence of nc-Si:Er thin films obtained by physical and chemical vapour deposition techniques: The effects of microstructure and chemical composition

    Energy Technology Data Exchange (ETDEWEB)

    Cerqueira, M.F., E-mail: fcerqueira@fisica.uminho.p [Departamento de Fisica, Universidade do Minho, Campus de Gualtar 4710-057 Braga (Portugal); Losurdo, M. [Institute of Inorganic Methodologies and of Plasmas, IMIP-CNR, Via Orabona n.4-70126 Bari (Italy); Stepikhova, M. [Institute for Physics of Microstructures RAS, 603600 Nizhnij Novgorod GSP-105 (Russian Federation); Alpuim, P.; Andres, G. [Departamento de Fisica, Universidade do Minho, Campus de Gualtar 4710-057 Braga (Portugal); Kozanecki, A. [Polish Academy of Sciences, Institute of Physics, PL-02668, Warsaw (Poland); Soares, M.J.; Peres, M. [Departamento de Fisica, Universidade de Aveiro, Campus de Santiago, 3700 Aveiro (Portugal)

    2009-08-31

    Erbium doped nanocrystalline silicon (nc-Si:Er) thin films were produced by reactive magnetron rf sputtering and by Er ion implantation into chemical vapor deposited Si films. The structure and chemical composition of films obtained by the two approaches were studied by micro-Raman scattering, spectroscopic ellipsometry and Rutherford backscattering techniques. Variation of deposition parameters was used to deposit films with different crystalline fraction and crystallite size. Photoluminescence measurements revealed a correlation between film microstructure and the Er{sup 3+} photoluminescence efficiency.

  5. Versatile Chemical Derivatizations to Design Glycol Chitosan-Based Drug Carriers

    Directory of Open Access Journals (Sweden)

    Sung Eun Kim

    2017-10-01

    Full Text Available Glycol chitosan (GC and its derivatives have been extensively investigated as safe and effective drug delivery carriers because of their unique physiochemical and biological properties. The reactive functional groups such as the amine and hydroxyl groups on the GC backbone allow for easy chemical modification with various chemical compounds (e.g., hydrophobic molecules, crosslinkers, and acid-sensitive and labile molecules, and the versatility in chemical modifications enables production of a wide range of GC-based drug carriers. This review summarizes the versatile chemical modification methods that can be used to design GC-based drug carriers and describes their recent applications in disease therapy.

  6. Electrolytic Manipulation of Persulfate Reactivity by Iron Electrodes for TCE Degradation in Groundwater

    Science.gov (United States)

    Yuan, Songhu; Liao, Peng; Alshawabkeh, Akram N.

    2014-01-01

    Activated persulfate oxidation is an effective in situ chemical oxidation process for groundwater remediation. However, reactivity of persulfate is difficult to manipulate or control in the subsurface causing activation before reaching the contaminated zone and leading to a loss of chemicals. Furthermore, mobilization of heavy metals by the process is a potential risk. An effective approach using iron electrodes is thus developed to manipulate the reactivity of persulfate in situ for trichloroethylene (TCE) degradation in groundwater, and to limit heavy metals mobilization. TCE degradation is quantitatively accelerated or inhibited by adjusting the current applied to the iron electrode, following k1 = 0.00053•Iv + 0.059 (−122 A/m3 ≤ Iv ≤ 244 A/m3) where k1 and Iv are the pseudo first-order rate constant (min−1) and volume normalized current (A/m3), respectively. Persulfate is mainly decomposed by Fe2+ produced from the electrochemical and chemical corrosion of iron followed by the regeneration via Fe3+ reduction on the cathode. SO4•− and •OH co-contribute to TCE degradation, but •OH contribution is more significant. Groundwater pH and oxidation-reduction potential can be restored to natural levels by the continuation of electrolysis after the disappearance of contaminants and persulfate, thus decreasing adverse impacts such as the mobility of heavy metals in the subsurface. PMID:24328192

  7. Reactivity on the Web

    OpenAIRE

    Bailey, James; Bry, François; Eckert, Michael; Patrânjan, Paula Lavinia

    2005-01-01

    Reactivity, the ability to detect simple and composite events and respond in a timely manner, is an essential requirement in many present-day information systems. With the emergence of new, dynamic Web applications, reactivity on the Web is receiving increasing attention. Reactive Web-based systems need to detect and react not only to simple events but also to complex, real-life situations. This paper introduces XChange, a language for programming reactive behaviour on the Web,...

  8. A fluorescence high throughput screening method for the detection of reactive electrophiles as potential skin sensitizers

    Energy Technology Data Exchange (ETDEWEB)

    Avonto, Cristina; Chittiboyina, Amar G. [National Center for Natural Products Research, Research Institute of Pharmaceutical Sciences, School of Pharmacy, The University of Mississippi, University, MS 38677 (United States); Rua, Diego [The Center for Food Safety and Applied Nutrition, US Food and Drug Administration, College Park, MD 20740 (United States); Khan, Ikhlas A., E-mail: ikhan@olemiss.edu [National Center for Natural Products Research, Research Institute of Pharmaceutical Sciences, School of Pharmacy, The University of Mississippi, University, MS 38677 (United States); Division of Pharmacognosy, Department of BioMolecular Sciences, School of Pharmacy, The University of Mississippi, University, MS 38677 (United States)

    2015-12-01

    Skin sensitization is an important toxicological end-point in the risk assessment of chemical allergens. Because of the complexity of the biological mechanisms associated with skin sensitization, integrated approaches combining different chemical, biological and in silico methods are recommended to replace conventional animal tests. Chemical methods are intended to characterize the potential of a sensitizer to induce earlier molecular initiating events. The presence of an electrophilic mechanistic domain is considered one of the essential chemical features to covalently bind to the biological target and induce further haptenation processes. Current in chemico assays rely on the quantification of unreacted model nucleophiles after incubation with the candidate sensitizer. In the current study, a new fluorescence-based method, ‘HTS-DCYA assay’, is proposed. The assay aims at the identification of reactive electrophiles based on their chemical reactivity toward a model fluorescent thiol. The reaction workflow enabled the development of a High Throughput Screening (HTS) method to directly quantify the reaction adducts. The reaction conditions have been optimized to minimize solubility issues, oxidative side reactions and increase the throughput of the assay while minimizing the reaction time, which are common issues with existing methods. Thirty-six chemicals previously classified with LLNA, DPRA or KeratinoSens™ were tested as a proof of concept. Preliminary results gave an estimated 82% accuracy, 78% sensitivity, 90% specificity, comparable to other in chemico methods such as Cys-DPRA. In addition to validated chemicals, six natural products were analyzed and a prediction of their sensitization potential is presented for the first time. - Highlights: • A novel fluorescence-based method to detect electrophilic sensitizers is proposed. • A model fluorescent thiol was used to directly quantify the reaction products. • A discussion of the reaction workflow

  9. A fluorescence high throughput screening method for the detection of reactive electrophiles as potential skin sensitizers

    International Nuclear Information System (INIS)

    Avonto, Cristina; Chittiboyina, Amar G.; Rua, Diego; Khan, Ikhlas A.

    2015-01-01

    Skin sensitization is an important toxicological end-point in the risk assessment of chemical allergens. Because of the complexity of the biological mechanisms associated with skin sensitization, integrated approaches combining different chemical, biological and in silico methods are recommended to replace conventional animal tests. Chemical methods are intended to characterize the potential of a sensitizer to induce earlier molecular initiating events. The presence of an electrophilic mechanistic domain is considered one of the essential chemical features to covalently bind to the biological target and induce further haptenation processes. Current in chemico assays rely on the quantification of unreacted model nucleophiles after incubation with the candidate sensitizer. In the current study, a new fluorescence-based method, ‘HTS-DCYA assay’, is proposed. The assay aims at the identification of reactive electrophiles based on their chemical reactivity toward a model fluorescent thiol. The reaction workflow enabled the development of a High Throughput Screening (HTS) method to directly quantify the reaction adducts. The reaction conditions have been optimized to minimize solubility issues, oxidative side reactions and increase the throughput of the assay while minimizing the reaction time, which are common issues with existing methods. Thirty-six chemicals previously classified with LLNA, DPRA or KeratinoSens™ were tested as a proof of concept. Preliminary results gave an estimated 82% accuracy, 78% sensitivity, 90% specificity, comparable to other in chemico methods such as Cys-DPRA. In addition to validated chemicals, six natural products were analyzed and a prediction of their sensitization potential is presented for the first time. - Highlights: • A novel fluorescence-based method to detect electrophilic sensitizers is proposed. • A model fluorescent thiol was used to directly quantify the reaction products. • A discussion of the reaction workflow

  10. Chemical protein synthesis: Inventing synthetic methods to decipher how proteins work.

    Science.gov (United States)

    Kent, Stephen

    2017-09-15

    Total chemical synthesis of proteins has been rendered practical by the chemical ligation principle: chemoselective condensation of unprotected peptide segments equipped with unique, mutually reactive functional groups, enabled by formation of a non-native replacement for the peptide bond. Ligation chemistries are briefly described, including native chemical ligation - thioester-mediated, amide-forming reaction at Xaa-Cys sites - and its extensions. Case studies from the author's own works are used to illustrate the utility and applications of chemical protein synthesis. Selected recent developments in the field are briefly discussed. Copyright © 2017 Elsevier Ltd. All rights reserved.

  11. 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

  12. 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.

  13. A BGK model for reactive mixtures of polyatomic gases with continuous internal energy

    Science.gov (United States)

    Bisi, M.; Monaco, R.; Soares, A. J.

    2018-03-01

    In this paper we derive a BGK relaxation model for a mixture of polyatomic gases with a continuous structure of internal energies. The emphasis of the paper is on the case of a quaternary mixture undergoing a reversible chemical reaction of bimolecular type. For such a mixture we prove an H -theorem and characterize the equilibrium solutions with the related mass action law of chemical kinetics. Further, a Chapman-Enskog asymptotic analysis is performed in view of computing the first-order non-equilibrium corrections to the distribution functions and investigating the transport properties of the reactive mixture. The chemical reaction rate is explicitly derived at the first order and the balance equations for the constituent number densities are derived at the Euler level.

  14. Non-equilibrium reactive flux: A unified framework for slow and fast reaction kinetics.

    Science.gov (United States)

    Bose, Amartya; Makri, Nancy

    2017-10-21

    The flux formulation of reaction rate theory is recast in terms of the expectation value of the reactive flux with an initial condition that corresponds to a non-equilibrium, factorized reactant density. In the common case of slow reactive processes, the non-equilibrium expression reaches the plateau regime only slightly slower than the equilibrium flux form. When the reactants are described by a single quantum state, as in the case of electron transfer reactions, the factorized reactant density describes the true initial condition of the reactive process. In such cases, the time integral of the non-equilibrium flux expression yields the reactant population as a function of time, allowing characterization of the dynamics in cases where there is no clear separation of time scales and thus a plateau regime cannot be identified. The non-equilibrium flux offers a unified approach to the kinetics of slow and fast chemical reactions and is ideally suited to mixed quantum-classical methods.

  15. 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.

  16. Coupled hydrogeological and reactive transport modelling of the Simpevarp area (Sweden)

    International Nuclear Information System (INIS)

    Molinero, Jorge; Raposo, Juan R.; Galindez, Juan M.; Arcos, David; Guimera, Jordi

    2008-01-01

    The Simpevarp area is one of the alternative sites being considered for the deep geological disposal of high level radioactive waste in Sweden. In this paper, a coupled regional groundwater flow and reactive solute transport model of the Simpevarp area is presented that integrates current hydrogeological and hydrochemical data of the area. The model simulates the current hydrochemical pattern of the groundwater system in the area. To that aim, a conceptual hydrochemical model was developed in order to represent the dominant chemical processes. Groundwater flow conditions were reproduced by taking into account fluid-density-dependent groundwater flow and regional hydrogeologic boundary conditions. Reactive solute transport calculations were performed on the basis of the velocity field so obtained. The model was calibrated and sensitivity analyses were carried out in order to investigate the effects of heterogeneities of hydraulic conductivity in the subsurface medium. Results provided by the reactive transport model are in good agreement with much of the measured hydrochemical data. This paper emphasizes the appropriateness of the use of reactive solute transport models when water-rock interaction reactions are involved, and demonstrates what powerful tools they are for the interpretation of hydrogeological and hydrochemical data from site geological repository characterization programs, by providing a qualitative framework for data analysis and testing of conceptual assumptions in a process-oriented approach

  17. Digital reactivity meter

    International Nuclear Information System (INIS)

    Jiang Zongbing

    1996-02-01

    The importance and the usual methods of reactivity measurement in a nuclear reactor are presented. Emphasis is put upon the calculation principle, software and hardware components, main specifications, application, as well as the features of the digital reactivity meter. The test results of operation in various reactors shown that the meter possess the following features: high accuracy, short response time, low output noise, high resolution, wide measuring range, simple and flexible to operate, high stability and reliability. In addition, the reactivity meter can save the measuring data automatically and have a perfect capability of self-verifying. It not only meet the requirement of the reactivity measurement in nuclear power plant, but also can be applied to various types of reactors. (1 tab.)

  18. Short communication: Reactivity of diacetyl with cleaning and sanitizing agents.

    Science.gov (United States)

    Rincon-Delgadillo, M I; Lopez-Hernandez, A; Rankin, S A

    2013-01-01

    Diacetyl is used to impart a buttery flavor to numerous food products such as sour cream, cottage cheese, vegetable oil-based spreads, baked goods, and beverages. Recent studies have linked exposure to high concentrations of diacetyl and the onset of bronchiolitis obliterans. Due to the reported risks that diacetyl may pose, many food companies have altered practices to reduce worker exposure to diacetyl, including the use of personal respirators, improved air handling systems, and adequate cleaning practices. Commonly used cleaning and sanitizing agents may be reactive with diacetyl; however, the efficacy of these chemicals has not been studied in detail and remains unclear. The objective of this work was to study the reaction chemistry of diacetyl with common industrial cleaning and sanitizing chemicals. The reactions were assessed at equimolar concentrations and analyzed by gas chromatography-mass spectrometry. Peroxyacetic acid was most reactive with diacetyl (95% reduction in diacetyl), followed by sodium hypochlorite (76% reduction), and hydrogen peroxide (26% reduction). Benzalkonium chloride (BAC) did not react with diacetyl. Acetic acid was detected as the main product of reactions of diacetyl with peroxyacetic acid, sodium hypochlorite, and hydrogen peroxide. 1,1-Dichloro-2-propanone and 1,1,1-trichloropropanone were also identified as volatile reaction products in the sodium hypochlorite reactions. Copyright © 2013 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

  19. Autonomic composite hydrogels by reactive printing: materials and oscillatory response.

    Science.gov (United States)

    Kramb, R C; Buskohl, P R; Slone, C; Smith, M L; Vaia, R A

    2014-03-07

    Autonomic materials are those that automatically respond to a change in environmental conditions, such as temperature or chemical composition. While such materials hold incredible potential for a wide range of uses, their implementation is limited by the small number of fully-developed material systems. To broaden the number of available systems, we have developed a post-functionalization technique where a reactive Ru catalyst ink is printed onto a non-responsive polymer substrate. Using a succinimide-amine coupling reaction, patterns are printed onto co-polymer or biomacromolecular films containing primary amine functionality, such as polyacrylamide (PAAm) or poly-N-isopropyl acrylamide (PNIPAAm) copolymerized with poly-N-(3-Aminopropyl)methacrylamide (PAPMAAm). When the films are placed in the Belousov-Zhabotinsky (BZ) solution medium, the reaction takes place only inside the printed nodes. In comparison to alternative BZ systems, where Ru-containing monomers are copolymerized with base monomers, reactive printing provides facile tuning of a range of hydrogel compositions, as well as enabling the formation of mechanically robust composite monoliths. The autonomic response of the printed nodes is similar for all matrices in the BZ solution concentrations examined, where the period of oscillation decreases in response to increasing sodium bromate or nitric acid concentration. A temperature increase reduces the period of oscillations and temperature gradients are shown to function as pace-makers, dictating the direction of the autonomic response (chemical waves).

  20. Fluid-rock interaction: A reactive transport approach

    Energy Technology Data Exchange (ETDEWEB)

    Steefel, C.; Maher, K.

    2009-04-01

    Fluid-rock interaction (or water-rock interaction, as it was more commonly known) is a subject that has evolved considerably in its scope over the years. Initially its focus was primarily on interactions between subsurface fluids of various temperatures and mostly crystalline rocks, but the scope has broadened now to include fluid interaction with all forms of subsurface materials, whether they are unconsolidated or crystalline ('fluid-solid interaction' is perhaps less euphonious). Disciplines that previously carried their own distinct names, for example, basin diagenesis, early diagenesis, metamorphic petrology, reactive contaminant transport, chemical weathering, are now considered to fall under the broader rubric of fluid-rock interaction, although certainly some of the key research questions differ depending on the environment considered. Beyond the broadening of the environments considered in the study of fluid-rock interaction, the discipline has evolved in perhaps an even more important way. The study of water-rock interaction began by focusing on geochemical interactions in the absence of transport processes, although a few notable exceptions exist (Thompson 1959; Weare et al. 1976). Moreover, these analyses began by adopting a primarily thermodynamic approach, with the implicit or explicit assumption of equilibrium between the fluid and rock. As a result, these early models were fundamentally static rather than dynamic in nature. This all changed with the seminal papers by Helgeson and his co-workers (Helgeson 1968; Helgeson et al. 1969) wherein the concept of an irreversible reaction path was formally introduced into the geochemical literature. In addition to treating the reaction network as a dynamically evolving system, the Helgeson studies introduced an approach that allowed for the consideration of a multicomponent geochemical system, with multiple minerals and species appearing as both reactants and products, at least one of which could be

  1. Monadic Functional Reactive Programming

    NARCIS (Netherlands)

    A.J. van der Ploeg (Atze); C Shan

    2013-01-01

    htmlabstractFunctional Reactive Programming (FRP) is a way to program reactive systems in functional style, eliminating many of the problems that arise from imperative techniques. In this paper, we present an alternative FRP formulation that is based on the notion of a reactive computation: a

  2. Insitu synthesis of self-assembled gold nanoparticles on glass or silicon substrates through reactive inkjet printing

    KAUST Repository

    Abulikemu, Mutalifu; Da'As, Eman Husni; Haverinen, Hanna M.; Cha, Dong Kyu; Malik, Mohammad A.; Jabbour, Ghassan Elie

    2013-01-01

    A facile and low cost method for the synthesis of self-assembled nanoparticles (NPs) with minimal size variation and chemical waste by using reactive inkjet printing was developed. Gold NPs with diameters as small as (8±2)nm can be made at low

  3. Reactivity costs in MARIA reactor

    International Nuclear Information System (INIS)

    Marcinkowska, Zuzanna E.; Pytel, Krzysztof M.; Frydrysiak, Andrzej

    2017-01-01

    Highlights: • The methodology for calculating consumed fuel cost of excess reactivity is proposed. • Correlation between time integral of the core excess reactivity and released energy. • Reactivity price gives number of fuel elements required for given excess reactivity. - Abstract: For the reactor operation at high power level and carrying out experiments and irradiations the major cost of reactor operation is the expense of nuclear fuel. In this paper the methodology for calculating consumed fuel cost-relatedness of excess reactivity is proposed. Reactivity costs have been determined on the basis of operating data. A number of examples of calculating the reactivity costs for processes such as: strong absorbing material irradiation, molybdenium-99 production, beryllium matrix poisoning and increased moderator temperature illustrates proposed method.

  4. Two new sources of reactive gaseous mercury in the free troposphere

    OpenAIRE

    H. Timonen; J. L. Ambrose; D. A. Jaffe

    2012-01-01

    Mercury (Hg) is a neurotoxin that bioaccumulates in the food chain. Mercury is emitted to the atmosphere primarily in its elemental form, which has a long lifetime allowing global transport. It is known that atmospheric oxidation of gaseous elemental mercury (GEM) generates reactive gaseous mercury (RGM) which plays an important role in the atmospheric mercury cycle by enhancing the rate of mercury deposition to ecosystems. However, the primary GEM oxidants, and the sources and chemical ...

  5. Non-equilibrium Quasi-Chemical Nucleation Model

    Science.gov (United States)

    Gorbachev, Yuriy E.

    2018-04-01

    Quasi-chemical model, which is widely used for nucleation description, is revised on the basis of recent results in studying of non-equilibrium effects in reacting gas mixtures (Kolesnichenko and Gorbachev in Appl Math Model 34:3778-3790, 2010; Shock Waves 23:635-648, 2013; Shock Waves 27:333-374, 2017). Non-equilibrium effects in chemical reactions are caused by the chemical reactions themselves and therefore these contributions should be taken into account in the corresponding expressions for reaction rates. Corrections to quasi-equilibrium reaction rates are of two types: (a) spatially homogeneous (caused by physical-chemical processes) and (b) spatially inhomogeneous (caused by gas expansion/compression processes and proportional to the velocity divergency). Both of these processes play an important role during the nucleation and are included into the proposed model. The method developed for solving the generalized Boltzmann equation for chemically reactive gases is applied for solving the set of equations of the revised quasi-chemical model. It is shown that non-equilibrium processes lead to essential deviation of the quasi-stationary distribution and therefore the nucleation rate from its traditional form.

  6. Reactive perforating collagenosis

    Directory of Open Access Journals (Sweden)

    Yadav Mukesh

    2009-01-01

    Full Text Available Reactive perforating collagenosis is a rare cutaneous disorder of unknown etiology. We hereby describe a case of acquired reactive perforating collagenosis in a patient of diabetes and chronic renal failure.

  7. Quantum chemical study of the structure, spectroscopy and reactivity of NO+.(H2O) n=1-5 clusters.

    Science.gov (United States)

    Linton, Kirsty A; Wright, Timothy G; Besley, Nicholas A

    2018-03-13

    Quantum chemical methods including Møller-Plesset perturbation (MP2) theory and density functional theory (DFT) have been used to study the structure, spectroscopy and reactivity of NO + (H 2 O) n =1-5 clusters. MP2/6-311++G** calculations are shown to describe the structure and spectroscopy of the clusters well. DFT calculations with exchange-correlation functionals with a low fraction of Hartree-Fock exchange give a binding energy of NO + (H 2 O) that is too high and incorrectly predict the lowest energy structure of NO + (H 2 O) 2 , and this error may be associated with a delocalization of charge onto the water molecule directly binding to NO + Ab initio molecular dynamics (AIMD) simulations were performed to study the NO + (H 2 O) 5 [Formula: see text] H + (H 2 O) 4 + HONO reaction to investigate the formation of HONO from NO + (H 2 O) 5 Whether an intracluster reaction to form HONO is observed depends on the level of electronic structure theory used. Of note is that methods that accurately describe the relative energies of the product and reactant clusters did not show reactions on the timescales studied. This suggests that in the upper atmosphere the reaction may occur owing to the energy present in the NO + (H 2 O) 5 complex following its formation.This article is part of the theme issue 'Modern theoretical chemistry'. © 2018 The Author(s).

  8. Physical-morphological and chemical changes leading to an increase in adhesion between plasma treated polyester fibres and a rubber matrix

    International Nuclear Information System (INIS)

    Krump, H.; Hudec, I.; Jasso, M.; Dayss, E.; Luyt, A.S.

    2006-01-01

    The effects of plasma treatment, used to increase adhesion strength between poly(ethylene terephtalate) (PET) fibres and a rubber matrix, were investigated and compared. Morphological changes as a result of atmospheric plasma treatment were observed using scanning electron microscopy (SEM) and atomic force microscopy (AFM). Wettability analysis using a surface energy evaluation system (SEE system) suggested that the plasma treated fibre was more wetting towards a polar liquid. When treated, these fibres showed a new lamellar crystallization, as shown by a new melting peak using differential scanning calorimetry (DSC). X-ray photoelectron spectroscopy (XPS) has been used to study the chemical effect of inert (argon), active and reactive (nitrogen and oxygen) microwave-plasma treatments of a PET surface. Reactive oxygen plasma treatment by a de-convolution method shows new chemical species that drastically alter the chemical reactivity of the PET surface. These studies have also shown that the surface population of chemical species formed after microwave-plasma treatment is dependent on the plasma gas. All these changes cause better adhesion strength of the PET fibres to the rubber matrix

  9. The Importance of Protons in Reactive Transport Modeling

    Science.gov (United States)

    McNeece, C. J.; Hesse, M. A.

    2014-12-01

    The importance of pH in aqueous chemistry is evident; yet, its role in reactive transport is complex. Consider a column flow experiment through silica glass beads. Take the column to be saturated and flowing with solution of a distinct pH. An instantaneous change in the influent solution pH can yield a breakthrough curve with both a rarefaction and shock component (composite wave). This behavior is unique among aqueous ions in transport and is more complex than intuition would tell. Analysis of the hyperbolic limit of this physical system can explain these first order transport phenomenon. This analysis shows that transport behavior is heavily dependent on the shape of the adsorption isotherm. Hence it is clear that accurate surface chemistry models are important in reactive transport. The proton adsorption isotherm has nonconstant concavity due to the proton's ability to partition into hydroxide. An eigenvalue analysis shows that an inflection point in the adsorption isotherm allows the development of composite waves. We use electrostatic surface complexation models to calculate realistic proton adsorption isotherms. Surface characteristics such as specific surface area, and surface site density were determined experimentally. We validate the model by comparison against silica glass bead flow through experiments. When coupled to surface complexation models, the transport equation captures the timing and behavior of breakthrough curves markedly better than with commonly used Langmuir assumptions. Furthermore, we use the adsorption isotherm to predict, a priori, the transport behavior of protons across pH composition space. Expansion of the model to multicomponent systems shows that proton adsorption can force composite waves to develop in the breakthrough curves of ions that would not otherwise exhibit such behavior. Given the abundance of reactive surfaces in nature and the nonlinearity of chemical systems, we conclude that building a greater understanding of

  10. Integrated Process Design, Control and Analysis of Intensified Chemical Processes

    DEFF Research Database (Denmark)

    Mansouri, Seyed Soheil

    chemical processes; for example, intensified processes such as reactive distillation. Most importantly, it identifies and eliminates potentially promising design alternatives that may have controllability problems later. To date, a number of methodologies have been proposed and applied on various problems......, that the same principles that apply to a binary non-reactive compound system are valid also for a binary-element or a multi-element system. Therefore, it is advantageous to employ the element based method for multicomponent reaction-separation systems. It is shown that the same design-control principles...

  11. Chemical reaction in MHD flow past a vertical plate with mass ...

    African Journals Online (AJOL)

    flow in a vertical double passage channel using Robin boundary conditions. ... the diffusion of a chemically reactive species in a laminar boundary layer flow. ...... hydrodynamic flow past a flat plate will Hall effects, Journal of the Physical.

  12. Steepest-entropy-ascent quantum thermodynamic modeling of the relaxation process of isolated chemically reactive systems using density of states and the concept of hypoequilibrium state

    Science.gov (United States)

    Li, Guanchen; von Spakovsky, Michael R.

    2016-01-01

    This paper presents a study of the nonequilibrium relaxation process of chemically reactive systems using steepest-entropy-ascent quantum thermodynamics (SEAQT). The trajectory of the chemical reaction, i.e., the accessible intermediate states, is predicted and discussed. The prediction is made using a thermodynamic-ensemble approach, which does not require detailed information about the particle mechanics involved (e.g., the collision of particles). Instead, modeling the kinetics and dynamics of the relaxation process is based on the principle of steepest-entropy ascent (SEA) or maximum-entropy production, which suggests a constrained gradient dynamics in state space. The SEAQT framework is based on general definitions for energy and entropy and at least theoretically enables the prediction of the nonequilibrium relaxation of system state at all temporal and spatial scales. However, to make this not just theoretically but computationally possible, the concept of density of states is introduced to simplify the application of the relaxation model, which in effect extends the application of the SEAQT framework even to infinite energy eigenlevel systems. The energy eigenstructure of the reactive system considered here consists of an extremely large number of such levels (on the order of 10130) and yields to the quasicontinuous assumption. The principle of SEA results in a unique trajectory of system thermodynamic state evolution in Hilbert space in the nonequilibrium realm, even far from equilibrium. To describe this trajectory, the concepts of subsystem hypoequilibrium state and temperature are introduced and used to characterize each system-level, nonequilibrium state. This definition of temperature is fundamental rather than phenomenological and is a generalization of the temperature defined at stable equilibrium. In addition, to deal with the large number of energy eigenlevels, the equation of motion is formulated on the basis of the density of states and a set of

  13. Natural abundance 15N NMR assignments delineate structural differences between intact and reactive-site hydrolyzed Cucurbita maxima trypsin inhibitor III.

    Science.gov (United States)

    Krishnamoorthi, R; Nemmers, S; Tobias, B

    1992-06-15

    15N NMR assignments were made to the backbone amide nitrogen atoms at natural isotopic abundance of intact and reactive-site (Arg5-Ile6) hydrolyzed Cucurbita maxima trypsin inhibitor III (CMTI-III and CMTI-III*, respectively) by means of 2D proton-detected heteronuclear single bond chemical shift correlation (HSBC) spectroscopy, utilizing the previously made sequence-specific 1H NMR assignments (Krishnamoorthi et al. (1992) Biochemistry 31, 898-904). Comparison of the 15N chemical shifts of the two forms of the inhibitor molecule revealed significant changes not only for residues located near the reactive-site region, but also for those distantly located. Residues Cys3, Arg5, Leu7, Met8, Cys10, Cys16, Glu19, His25, Tyr27, Cys28 and Gly29 showed significant chemical shift changes ranging from 0.3 to 6.1 ppm, thus indicating structural perturbations that were transmitted throughout the molecule. These findings confirm the earlier conclusions based on 1H NMR investigations.

  14. What makes ecological systems reactive?

    Science.gov (United States)

    Snyder, Robin E

    2010-06-01

    Although perturbations from a stable equilibrium must ultimately vanish, they can grow initially, and the maximum initial growth rate is called reactivity. Reactivity thus identifies systems that may undergo transient population surges or drops in response to perturbations; however, we lack biological and mathematical intuition about what makes a system reactive. This paper presents upper and lower bounds on reactivity for an arbitrary linearized model, explores their strictness, and discusses their biological implications. I find that less stable systems (i.e. systems with long transients) have a smaller possible range of reactivities for which no perturbations grow. Systems with more species have a higher capacity to be reactive, assuming species interactions do not weaken too rapidly as the number of species increases. Finally, I find that in discrete time, reactivity is determined largely by mean interaction strength and neither discrete nor continuous time reactivity are sensitive to food web topology. 2010 Elsevier Inc. All rights reserved.

  15. On microscopic simulations of systems with model chemical reactions

    International Nuclear Information System (INIS)

    Gorecki, J.; Gorecka, J.N.

    1998-01-01

    Large scale computer simulations of model chemical systems play the role of idealized experiments in which theories may be tested. In this paper we present two applications of microscopic simulations based on the reactive hard sphere model. We investigate the influence of internal fluctuations on an oscillating chemical system and observe how they modify the phase portrait of it. Another application, we consider, is concerned with the propagation of a chemical wave front associated with a thermally activated reaction. It is shown that the nonequilibrium effects increase the front velocity if compared with the velocity of the front generated by a nonactivated process characterized by the same rate constant. (author)

  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. Sequence homology: A poor predictive value for profilins cross-reactivity

    Directory of Open Access Journals (Sweden)

    Pazouki Nazanin

    2005-09-01

    Full Text Available Summary Background Profilins are highly cross-reactive allergens which bind IgE antibodies of almost 20% of plant-allergic patients. This study is aimed at investigating cross-reactivity of melon profilin with other plant profilins and the role of the linear and conformational epitopes in human IgE cross-reactivity. Methods Seventeen patients with melon allergy were selected based on clinical history and a positive skin prick test to melon extract. Melon profilin has been cloned and expressed in E. coli. The IgE binding and cross-reactivity of the recombinant profilin were measured by ELISA and inhibition ELISA. The amino acid sequence of melon profilin was compared with other profilin sequences. A combination of chemical cleavage and immunoblotting techniques were used to define the role of conformational and linear epitopes in IgE binding. Comparative modeling was used to construct three-dimensional models of profilins and to assess theoretical impact of amino acid differences on conformational structure. Results Profilin was identified as a major IgE-binding component of melon. Alignment of amino acid sequences of melon profilin with other profilins showed the most identity with watermelon profilin. This melon profilin showed substantial cross-reactivity with the tomato, peach, grape and Cynodon dactylon (Bermuda grass pollen profilins. Cantaloupe, watermelon, banana and Poa pratensis (Kentucky blue grass displayed no notable inhibition. Our experiments also indicated human IgE only react with complete melon profilin. Immunoblotting analysis with rabbit polyclonal antibody shows the reaction of the antibody to the fragmented and complete melon profilin. Although, the well-known linear epitope of profilins were identical in melon and watermelon, comparison of three-dimensional models of watermelon and melon profilins indicated amino acid differences influence the electric potential and accessibility of the solvent-accessible surface of

  18. Photofunctional Co-Cr Alloy Generating Reactive Oxygen Species for Photodynamic Applications

    Directory of Open Access Journals (Sweden)

    Kang-Kyun Wang

    2013-01-01

    Full Text Available We report the fabrication of photofunctional Co-Cr alloy plate that is prepared by a simple modification process for photodynamic application. Photoinduced functionality is provided by the photosensitizer of hematoporphyrin (Hp that initially generates reactive oxygen species (ROS such as superoxide anion radical and singlet oxygen. The photosensitizer with carboxyl group was chemically bonded to the surface of the Co-Cr alloy plate by esterification reaction. Microstructure and elemental composition of the Co-Cr alloy plate were checked with scanning electron microscopy (SEM and energy dispersive X-ray spectrometer (EDS. Fabrication of the photofunctionality of the Co-Cr alloy plate was confirmed with X-ray photoelectron spectroscopy (XPS, reflectance UV-Vis absorption, and emission spectroscopy. Reactive oxygen generation from the photofunctional Co-Cr alloy plate was confirmed by using the decomposition reaction of 1,3-diphenylisobenzofuran (DPBF. The results suggest that the immobilized photosensitizer molecules on the surface of Co-Cr alloy plate still possess their optical and functional properties including reactive oxygen generation. To open the possibility for its application as a photodynamic material to biological system, the fabricated photofunctional Co-Cr alloy is applied to the decomposition of smooth muscle cells.

  19. Electronic structures and water reactivity of mixed metal sulfide cluster anions

    Energy Technology Data Exchange (ETDEWEB)

    Saha, Arjun; Raghavachari, Krishnan [Department of Chemistry, Indiana University, Bloomington, Indiana 47405 (United States)

    2014-08-21

    The electronic structures and chemical reactivity of the mixed metal sulfide cluster anion (MoWS{sub 4}{sup −}) have been investigated with density functional theory. Our study reveals the presence of two almost isoenergetic structural isomers, both containing two bridging sulfur atoms in a quartet state. However, the arrangement of the terminal sulfur atoms is different in the two isomers. In one isomer, the two metals are in the same oxidation state (each attached to one terminal S). In the second isomer, the two metals are in different oxidation states (with W in the higher oxidation state attached to both terminal S). The reactivity of water with the two lowest energy isomers has also been studied, with an emphasis on pathways leading to H{sub 2} release. The reactive behavior of the two isomers is different though the overall barriers in both systems are small. The origin of the differences are analyzed and discussed. The reaction pathways and barriers are compared with the corresponding behavior of monometallic sulfides (Mo{sub 2}S{sub 4}{sup −} and W{sub 2}S{sub 4}{sup −}) as well as mixed metal oxides (MoWO{sub 4}{sup −})

  20. Radiation induced functionalism of polyethylene and ground tire rubber for their reactive compatibility in thermoplastic elastomers

    Energy Technology Data Exchange (ETDEWEB)

    Fainleib, A.; Grigoryeva, O. [Institute of Macromolecular Chemistry, National Academy of Sciences of Ukraine, Kiev 02160 (Ukraine); Martinez B, G. [Laboratorio de Investigacion y Desarrollo de Materiales Avanzados, Facultad de Quimica, Universidad Autonoma del Estado de Mexico, Km. 12 Carretera Toluca-Atlacomulco, San Cayetano 50200, Estado de Mexico (Mexico)], e-mail: fainleib@i.kiev.ua

    2009-07-01

    Reactive compatibility of recycled low-or high-density polyethylenes (LDPE and HDPE, respectively) and ground tire rubber (GTR) via chemical interactions of pre-functionalized components in their blend interface has been carried out. Polyethylene component was functionalized with maleic anhydride (MAH) as well as the rubber component was modified via functionalism with MAH or acrylamide using chemically or irradiation ({gamma} rays) induced grafting techniques. Additional coupling agents such as-p-phenylene diamine (PDA) and polyamide fiber (PAF, from fiber wastes) were used for some thermoplastic elastomer (TPE) producing. The grafting degree and molecular mass distribution of the chromatography analyses, respectively. TPE materials based on synthesized reactive polyethylenes and GTR as well as ethylene-propylene-diene monomer rubber were prepared by dynamic vulcanization of the rubber phase inside thermoplastic (polyethylene) matrix and their phase structure, and main properties have been studied using DSC, TGA, DMTA and mechanical testing. As a final result, the high performance TPE with improved mechanical properties has been developed. (Author)

  1. Computational thermal, chemical, fluid, and solid mechanics for geosystems management.

    Energy Technology Data Exchange (ETDEWEB)

    Davison, Scott; Alger, Nicholas; Turner, Daniel Zack; Subia, Samuel Ramirez; Carnes, Brian; Martinez, Mario J.; Notz, Patrick K.; Klise, Katherine A.; Stone, Charles Michael; Field, Richard V., Jr.; Newell, Pania; Jove-Colon, Carlos F.; Red-Horse, John Robert; Bishop, Joseph E.; Dewers, Thomas A.; Hopkins, Polly L.; Mesh, Mikhail; Bean, James E.; Moffat, Harry K.; Yoon, Hongkyu

    2011-09-01

    This document summarizes research performed under the SNL LDRD entitled - Computational Mechanics for Geosystems Management to Support the Energy and Natural Resources Mission. The main accomplishment was development of a foundational SNL capability for computational thermal, chemical, fluid, and solid mechanics analysis of geosystems. The code was developed within the SNL Sierra software system. This report summarizes the capabilities of the simulation code and the supporting research and development conducted under this LDRD. The main goal of this project was the development of a foundational capability for coupled thermal, hydrological, mechanical, chemical (THMC) simulation of heterogeneous geosystems utilizing massively parallel processing. To solve these complex issues, this project integrated research in numerical mathematics and algorithms for chemically reactive multiphase systems with computer science research in adaptive coupled solution control and framework architecture. This report summarizes and demonstrates the capabilities that were developed together with the supporting research underlying the models. Key accomplishments are: (1) General capability for modeling nonisothermal, multiphase, multicomponent flow in heterogeneous porous geologic materials; (2) General capability to model multiphase reactive transport of species in heterogeneous porous media; (3) Constitutive models for describing real, general geomaterials under multiphase conditions utilizing laboratory data; (4) General capability to couple nonisothermal reactive flow with geomechanics (THMC); (5) Phase behavior thermodynamics for the CO2-H2O-NaCl system. General implementation enables modeling of other fluid mixtures. Adaptive look-up tables enable thermodynamic capability to other simulators; (6) Capability for statistical modeling of heterogeneity in geologic materials; and (7) Simulator utilizes unstructured grids on parallel processing computers.

  2. Spectroscopic Evidence of the Improvement of Reactive Iron Mineral Content in Red Soil by Long-Term Application of Swine Manure.

    Directory of Open Access Journals (Sweden)

    Chichao Huang

    Full Text Available Mineral elements in soil solutions are thought to be the precursor of the formation of reactive minerals, which play an important role in global carbon (C cycling. However, information regarding the regulation of mineral elements release in soil is scarce. Here, we examined the long-term (i.e., 23 yrs effects of fertilisation practices on Fe minerals in a red soil in Southern China. The results from chemical analysis and Fourier-transform infrared spectroscopy showed that long-term swine manure (M treatment released greater amounts of minerals into soil solutions than chemical fertilisers (NPK treatment, and Fe played a dominant role in the preservation of dissolved organic C. Furthermore, Fe K-edge X-ray absorption near-edge fine structure spectroscopy demonstrated that reactive Fe minerals were mainly composed of less crystalline ferrihydrite in the M-treated soil and more crystalline goethite in the NPK-treated soil. In conclusion, this study reported spectroscopic evidence of the improvement of reactive Femineral content in the M-treated soil colloids when compared to NPK-treated soil colloids.

  3. Reactive power compensator

    Science.gov (United States)

    El-Sharkawi, Mohamed A.; Venkata, Subrahmanyam S.; Chen, Mingliang; Andexler, George; Huang, Tony

    1992-01-01

    A system and method for determining and providing reactive power compensation for an inductive load. A reactive power compensator (50,50') monitors the voltage and current flowing through each of three distribution lines (52a, 52b, 52c), which are supplying three-phase power to one or more inductive loads. Using signals indicative of the current on each of these lines when the voltage waveform on the line crosses zero, the reactive power compensator determines a reactive power compensator capacitance that must be connected to the lines to maintain a desired VAR level, power factor, or line voltage. Alternatively, an operator can manually select a specific capacitance for connection to each line, or the capacitance can be selected based on a time schedule. The reactive power compensator produces control signals, which are coupled through optical fibers (102/106) to a switch driver (110, 110') to select specific compensation capacitors (112) for connections to each line. The switch driver develops triggering signals that are supplied to a plurality of series-connected solid state switches (350), which control charge current in one direction in respect to ground for each compensation capacitor. During each cycle, current flows from ground to charge the capacitors as the voltage on the line begins to go negative from its positive peak value. The triggering signals are applied to gate the solid state switches into a conducting state when the potential on the lines and on the capacitors reaches a negative peak value, thereby minimizing both the potential difference and across the charge current through the switches when they begin to conduct. Any harmonic distortion on the potential and current carried by the lines is filtered out from the current and potential signals used by the reactive power compensator so that it does not affect the determination of the required reactive compensation.

  4. Reactive power compensator

    Energy Technology Data Exchange (ETDEWEB)

    El-Sharkawi, Mohamed A. (Renton, WA); Venkata, Subrahmanyam S. (Woodinville, WA); Chen, Mingliang (Kirkland, WA); Andexler, George (Everett, WA); Huang, Tony (Seattle, WA)

    1992-01-01

    A system and method for determining and providing reactive power compensation for an inductive load. A reactive power compensator (50,50') monitors the voltage and current flowing through each of three distribution lines (52a, 52b, 52c), which are supplying three-phase power to one or more inductive loads. Using signals indicative of the current on each of these lines when the voltage waveform on the line crosses zero, the reactive power compensator determines a reactive power compensator capacitance that must be connected to the lines to maintain a desired VAR level, power factor, or line voltage. Alternatively, an operator can manually select a specific capacitance for connection to each line, or the capacitance can be selected based on a time schedule. The reactive power compensator produces control signals, which are coupled through optical fibers (102/106) to a switch driver (110, 110') to select specific compensation capacitors (112) for connections to each line. The switch driver develops triggering signals that are supplied to a plurality of series-connected solid state switches (350), which control charge current in one direction in respect to ground for each compensation capacitor. During each cycle, current flows from ground to charge the capacitors as the voltage on the line begins to go negative from its positive peak value. The triggering signals are applied to gate the solid state switches into a conducting state when the potential on the lines and on the capacitors reaches a negative peak value, thereby minimizing both the potential difference and across the charge current through the switches when they begin to conduct. Any harmonic distortion on the potential and current carried by the lines is filtered out from the current and potential signals used by the reactive power compensator so that it does not affect the determination of the required reactive compensation.

  5. Digital reactivity meter

    International Nuclear Information System (INIS)

    Copie, M.; Valantic, B.

    1978-01-01

    Digital reactivity meters (DRM) are mostly used as measuring instruments, e.g. for calibration of control rods, and there are only a few cases of their incorporation into the control systems of the reactors. To move in this direction there is more development work needed. First of all, fast algorithms are needed for inverse kinetics equations to relieve the computer for more important tasks of reactor model solving in real time. The next problem, currently under investigation, is the incorporation of the reactor thermal-hydraulic model into the DRM so that it can be used in the power range. Such an extension of DHM allows presentation not only of the instantaneous reactivity of the system, but also the inserted reactivity can be estimated from the temperature reactivity feed-backs. One of the applications of this concept is the anomalous digital reactivity monitor (ADRN) as part of the reactor protection system. As a solution of the first problem, a fast algorithm for solving the inverse kinetics equations has been implemented in the off-line program RODCAL on CDC 1700 computer and tested for its accuracy by performing different control rod calibrations on the reactor TRIGA

  6. ROLE OF STEM CELL FACTOR IN THE REACTIVATION OF HUMAN FETAL HEMOGLOBIN

    Directory of Open Access Journals (Sweden)

    Marco Gabbianelli

    2009-11-01

    In vitro and in vivo models have led to the identification of several chemical compounds able to reactivate HbF synthesis in adult erythroid cells. Although the impact of these HbF inducers, including hypomethylating agents, histone deacetylase inhibitors and hydroxyurea, was clear on the natural history of sickle cell anemia, the benefit on the clinical course of -thalassemia was only limited: particularly, the toxicity and the modest increase in γ-globin reactivation indicated the need for improved agents able to induce higher levels of HbF. In the present review we describe the biologic properties of Stem Cell Factor (SCF, a cytokine sustaining the survival and proliferation of erythroid cells, that at pharmacological doses acts as a potent stimulator of HbF synthesis in adult erythroid cells.

  7. Revisiting the definition of the electronic chemical potential, chemical hardness, and softness at finite temperatures

    Energy Technology Data Exchange (ETDEWEB)

    Franco-Pérez, Marco, E-mail: qimfranco@hotmail.com, E-mail: jlgm@xanum.uam.mx [Departamento de Química, Universidad Autónoma Metropolitana-Iztapalapa, Av. San Rafael Atlixco 186, México D. F. 09340 (Mexico); Department of Chemistry, McMaster University, Hamilton, Ontario L8S 4M1 (Canada); Gázquez, José L., E-mail: qimfranco@hotmail.com, E-mail: jlgm@xanum.uam.mx [Departamento de Química, Universidad Autónoma Metropolitana-Iztapalapa, Av. San Rafael Atlixco 186, México D. F. 09340 (Mexico); Ayers, Paul W. [Department of Chemistry, McMaster University, Hamilton, Ontario L8S 4M1 (Canada); Vela, Alberto [Departamento de Química, Centro de Investigación y de Estudios Avanzados (Cinvestav), Av. Instituto Politécnico Nacional 2508, México D. F. 07360 (Mexico)

    2015-10-21

    We extend the definition of the electronic chemical potential (μ{sub e}) and chemical hardness (η{sub e}) to finite temperatures by considering a reactive chemical species as a true open system to the exchange of electrons, working exclusively within the framework of the grand canonical ensemble. As in the zero temperature derivation of these descriptors, the response of a chemical reagent to electron-transfer is determined by the response of the (average) electronic energy of the system, and not by intrinsic thermodynamic properties like the chemical potential of the electron-reservoir which is, in general, different from the electronic chemical potential, μ{sub e}. Although the dependence of the electronic energy on electron number qualitatively resembles the piecewise-continuous straight-line profile for low electronic temperatures (up to ca. 5000 K), the introduction of the temperature as a free variable smoothens this profile, so that derivatives (of all orders) of the average electronic energy with respect to the average electron number exist and can be evaluated analytically. Assuming a three-state ensemble, well-known results for the electronic chemical potential at negative (−I), positive (−A), and zero values of the fractional charge (−(I + A)/2) are recovered. Similarly, in the zero temperature limit, the chemical hardness is formally expressed as a Dirac delta function in the particle number and satisfies the well-known reciprocity relation with the global softness.

  8. Modeling the transport of chemical warfare agents and simulants in polymeric substrates for reactive decontamination

    Science.gov (United States)

    Pearl, Thomas; Mantooth, Brent; Varady, Mark; Willis, Matthew

    2014-03-01

    Chemical warfare agent simulants are often used for environmental testing in place of highly toxic agents. This work sets the foundation for modeling decontamination of absorbing polymeric materials with the focus on determining relationships between agents and simulants. The correlations of agents to simulants must consider the three way interactions in the chemical-material-decontaminant system where transport and reaction occur in polymer materials. To this end, diffusion modeling of the subsurface transport of simulants and live chemical warfare agents was conducted for various polymer systems (e.g., paint coatings) with and without reaction pathways with applied decontamination. The models utilized 1D and 2D finite difference diffusion and reaction models to simulate absorption and reaction in the polymers, and subsequent flux of the chemicals out of the polymers. Experimental data including vapor flux measurements and dynamic contact angle measurements were used to determine model input parameters. Through modeling, an understanding of the relationship of simulant to live chemical warfare agent was established, focusing on vapor emission of agents and simulants from materials.

  9. Ecofriendly degradation of sulfonated diazo dye C.I. Reactive Green 19A using Micrococcus glutamicus NCIM-2168.

    Science.gov (United States)

    Saratale, R G; Saratale, G D; Chang, J S; Govindwar, S P

    2009-09-01

    Micrococcus glutamicus NCIM-2168 exhibited complete decolorization and degradation of C.I. Reactive Green 19A (an initial concentration of 50 mg l(-1)) within 42 h at temperature 37 degrees C and pH 8, under static condition. Extent of mineralization was determined with total organic carbon (TOC) and chemical oxygen demand (COD) measurement, showing a satisfactory reduction of TOC (72%) and COD (66%) within 42 h. Enzyme studies shows involvement of oxidoreductive enzymes in decolorization/degradation process. Analytical studies of the extracted metabolites confirmed the significant degradation of Reactive Green 19A into various metabolites. The microbial toxicity and phytotoxicity assay revealed that the degradation of Reactive Green 19A produced nontoxic metabolites. In addition, the M. glutamicus strain was applied to decolorize a mixture of ten reactive dyes showing a 63% decolorization (in terms of decrease in ADMI value) within 72 h, along with 48% and 42% reduction in TOC and COD under static condition.

  10. Understanding the mechanism of catalytic fast pyrolysis by unveiling reactive intermediates in heterogeneous catalysis

    Science.gov (United States)

    Hemberger, Patrick; Custodis, Victoria B. F.; Bodi, Andras; Gerber, Thomas; van Bokhoven, Jeroen A.

    2017-06-01

    Catalytic fast pyrolysis is a promising way to convert lignin into fine chemicals and fuels, but current approaches lack selectivity and yield unsatisfactory conversion. Understanding the pyrolysis reaction mechanism at the molecular level may help to make this sustainable process more economic. Reactive intermediates are responsible for product branching and hold the key to unveiling these mechanisms, but are notoriously difficult to detect isomer-selectively. Here, we investigate the catalytic pyrolysis of guaiacol, a lignin model compound, using photoelectron photoion coincidence spectroscopy with synchrotron radiation, which allows for isomer-selective detection of reactive intermediates. In combination with ambient pressure pyrolysis, we identify fulvenone as the central reactive intermediate, generated by catalytic demethylation to catechol and subsequent dehydration. The fulvenone ketene is responsible for the phenol formation. This technique may open unique opportunities for isomer-resolved probing in catalysis, and holds the potential for achieving a mechanistic understanding of complex, real-life catalytic processes.

  11. Immobilization of cesium in cement containing reactive silica and pozzolans

    International Nuclear Information System (INIS)

    McCulloch, C.E.; Angus, M.J.; Glasser, F.P.; Rahman, A.A.

    1984-01-01

    High surface area silicas, ground blast furnace slag, fly ash, and natural pozzolan markedly enhance the sorption of Cs in cement-based systems. Fly ash low in alkali and silicas are considered to be most suitable for Cs immobilization. Since these materials are chemically reactive with the cement components, the optimal level of addition must be sufficiently high, probably 20-30 wt%, to provide a permanent excess of sorbent. The sorptive mechanism is demonstrated and shown to be enhanced by the alkaline cement environment

  12. Chemosensory perception, symptoms and autonomic responses during chemical exposure in multiple chemical sensitivity

    DEFF Research Database (Denmark)

    Andersson, Linus; Claeson, Anna Sara; Dantoft, Thomas Meinertz

    2016-01-01

    Purpose: Multiple chemical sensitivity (MCS) is a prevalent medically unexplained symptom characterized by symptom reactions to everyday chemical exposure below hygienic thresholds. The aim of this study was to investigate the expressions of hyper-reactivity in MCS during whole-body exposure to low...... concentrations of the odorant n-butanol. Methods: We exposed 18 participants with MCS and 18 non-ill controls to a low concentration of the odorant n-butanol using an exposure chamber. The first 10 min constituted blank exposure, after which the n-butanol concentration increased and reached a plateau at 11.5 mg....../m3. Results: MCS participants, compared with controls, reported greater perceived odor intensities, more unpleasantness to the exposure and increasing symptoms over time. MCS participants also expressed higher pulse rate and lower pulse rate variability than controls did. No group differences were...

  13. Modeling of Toxicity-Relevant Electrophilic Reactivity for Guanine with Epoxides: Estimating the Hard and Soft Acids and Bases (HSAB) Parameter as a Predictor.

    Science.gov (United States)

    Zhang, Jing; Wang, Chenchen; Ji, Li; Liu, Weiping

    2016-05-16

    According to the electrophilic theory in toxicology, many chemical carcinogens in the environment and/or their active metabolites are electrophiles that exert their effects by forming covalent bonds with nucleophilic DNA centers. The theory of hard and soft acids and bases (HSAB), which states that a toxic electrophile reacts preferentially with a biological macromolecule that has a similar hardness or softness, clarifies the underlying chemistry involved in this critical event. Epoxides are hard electrophiles that are produced endogenously by the enzymatic oxidation of parent chemicals (e.g., alkenes and PAHs). Epoxide ring opening proceeds through a SN2-type mechanism with hard nucleophile DNA sites as the major facilitators of toxic effects. Thus, the quantitative prediction of chemical reactivity would enable a predictive assessment of the molecular potential to exert electrophile-mediated toxicity. In this study, we calculated the activation energies for reactions between epoxides and the guanine N7 site for a diverse set of epoxides, including aliphatic epoxides, substituted styrene oxides, and PAH epoxides, using a state-of-the-art density functional theory (DFT) method. It is worth noting that these activation energies for diverse epoxides can be further predicted by quantum chemically calculated nucleophilic indices from HSAB theory, which is a less computationally demanding method than the exacting procedure for locating the transition state. More importantly, the good qualitative/quantitative correlations between the chemical reactivity of epoxides and their bioactivity suggest that the developed model based on HSAB theory may aid in the predictive hazard evaluation of epoxides, enabling the early identification of mutagenicity/carcinogenicity-relevant SN2 reactivity.

  14. Combustion behaviour of ultra clean coal obtained by chemical demineralisation

    Energy Technology Data Exchange (ETDEWEB)

    F. Rubiera; A. Arenillas; B. Arias; J.J. Pis; I. Suarez-Ruiz; K.M. Steel; J.W. Patrick [Instituto Nacional del Carbon, CSIC, Oviedo (Spain)

    2003-10-01

    The increasing environmental concern caused by the use of fossil fuels and the concomitant need for improved combustion efficiency is leading to the development of new coal cleaning and utilisation processes. However, the benefits achieved by the removal of most mineral matter from coal either by physical or chemical methods can be annulled if poor coal combustibility characteristics are attained. In this work a high volatile bituminous coal with 6% ash content was subjected to chemical demineralisation via hydrofluoric and nitric acid leaching, the ash content of the clean coal was reduced to 0.3%. The original and treated coals were devolatilised in a drop tube furnace and the structure and morphology of the resultant chars was analysed by optical and scanning electron microscopies. The reactivity characteristics of the chars were studied by isothermal combustion tests in air at different temperatures in a thermogravimetric system. Comparison of the combustion behaviour and pollutant emissions of both coals was conducted in a drop tube furnace operating at 1000{sup o}C. The results of this work indicate that the char obtained from the chemically treated coal presents very different structure, morphology and reactivity behaviour than the char from the original coal. The changes induced by the chemical treatment increased the combustion efficiency determined in the drop tube furnace, in fact higher burnout levels were obtained for the demineralised coal.

  15. Integrated Design and Control of Reactive and Non-Reactive Distillation Processes

    DEFF Research Database (Denmark)

    Mansouri, Seyed Soheil; Sales-Cruz, Mauricio; Huusom, Jakob Kjøbsted

    , an alternative approach is to tackle process design and controllability issues simultaneously, in the early stages of process design. This simultaneous synthesis approach provides optimal/near optimal operation and more efficient control of conventional (non-reactive binary distillation columns) (Hamid et al...... of methodologies have been proposed and applied on various problems to address the interactions between process design and control, and they range from optimization-based approaches to model-based methods (Sharifzadeh, 2013). In this work, integrated design and control of non-reactive distillation, ternary...... reactive distillation processes. The element concept (Pérez Cisneros et al., 1997) is used to translate a ternary system of compounds (A + B ↔ C) to a binary system of element (WA and WB). In the case of multicomponent reactive distillation processes the equivalent element concept is used to translate...

  16. Programming Reactive Extensions and LINQ

    CERN Document Server

    Liberty, Jesse

    2011-01-01

    Pro Reactive Extensions and LINQ is a deep dive into the next important technology for .NET developers: Reactive Extensions. This in-depth tutorial goes beyond what is available anywhere else to teach how to write WPF, Silverlight, and Windows Phone applications using the Reactive Extensions (Rx) to handle events and asynchronous method calls. Reactive programming allows you to turn those aspects of your code that are currently imperative into something much more event-driven and flexible. For this reason, it's sometimes referred to as LINQ for Events. Reactive programming hinges on the concep

  17. Analysis of the trend to equilibrium of a chemically reacting system

    International Nuclear Information System (INIS)

    Kremer, Gilberto M; Bianchi, Miriam Pandolfi; Soares, Ana Jacinta

    2007-01-01

    In this present paper, a quaternary gaseous reactive mixture, for which the chemical reaction is close to its final stage and the elastic and reactive frequencies are comparable, is modelled within the Boltzmann equation extended to reacting gases. The main objective is a detailed analysis of the non-equilibrium effects arising in the reactive system A 1 + A 2 ↔ A 3 + A 4 , in a flow regime which is considered not far away from thermal, mechanical and chemical equilibrium. A first-order perturbation solution technique is applied to the macroscopic field equations for the spatially homogeneous gas system, and the trend to equilibrium is studied in detail. Adopting elastic hard-spheres and reactive line-of-centres cross sections and an appropriate choice of the input distribution functions-which allows us to distinguish the two cases where the constituents are either at same or different temperatures-explicit computations of the linearized production terms for mass, momentum and total energy are performed for each gas species. The departures from the equilibrium states of densities, temperatures and diffusion fluxes are characterized by small perturbations of their corresponding equilibrium values. For the hydrogen-chlorine system, the perturbations are plotted as functions of time for both cases where the species are either at the same or different temperatures. Moreover, the trend to equilibrium of the reaction rates is represented for the forward and backward reaction H 2 + Cl ↔ HCl + H

  18. Chemical Ligation Reactions of Oligonucleotides for Biological and Medicinal Applications.

    Science.gov (United States)

    Abe, Hiroshi; Kimura, Yasuaki

    2018-01-01

    Chemical ligation of oligonucleotides (ONs) is the key reaction for various ON-based technologies. We have tried to solve the problems of RNA interference (RNAi) technology by applying ON chemical ligation to RNAi. We designed a new RNAi system, called intracellular buildup RNAi (IBR-RNAi), where the RNA fragments are built up into active small-interference RNA (siRNA) in cells through a chemical ligation reaction. Using the phosphorothioate and iodoacetyl groups as reactive functional groups for the ligation, we achieved RNAi effects without inducing immune responses. Additionally, we developed a new chemical ligation for IBR-RNAi, which affords a more native-like structure in the ligated product. The new ligation method should be useful not only for IBR-RNAi but also for the chemical synthesis of biofunctional ONs.

  19. METHODS TO IMPROVE LIGNIN’S REACTIVITY AS A PHENOL SUBSTITUTE AND AS REPLACEMENT FOR OTHER PHENOLIC COMPOUNDS: A BRIEF REVIEW

    OpenAIRE

    Yonghong Zhou; Meng Zhang; Hui Pan; Lihong Hu

    2011-01-01

    Lignin is readily available as a by-product from the pulp and paper industry. It is considered to be a promising substitute for phenol in phenol-formaldehyde (PF) resin synthesis, given the increasing concerns of the shortage of fossil resources and the environmental impact from petroleum-based products. One hurdle that prevents the commercial utilization of lignin is its low reactivity due to its chemical structure. Many efforts have been made to improve its reactivity by modification and/or...

  20. Chemical consequences of nuclear transformations

    International Nuclear Information System (INIS)

    Collins, C.H.; Lancas, F.M.; Andrade, J.C. de; Collins, K.E.

    1979-01-01

    The recombination processes of chemical bonds in liquid phase, after being split by nuclear transformations, include hot and diffuse reactions. Both processes probably occur by different mechanisms. The direct substitution process as well as processes which involve atoms, ions or other fragments retained in 'cages' formed by surrounding molecules, are processes not sensitive to the presence of a sequestering agent. The diffuse reactions whose fragments escaped from the 'cage' involve reactions with any reactive species found in the medium. (Author) [pt

  1. Non-equilibrium reaction rates in chemical kinetic equations

    Science.gov (United States)

    Gorbachev, Yuriy

    2018-05-01

    Within the recently proposed asymptotic method for solving the Boltzmann equation for chemically reacting gas mixture, the chemical kinetic equations has been derived. Corresponding one-temperature non-equilibrium reaction rates are expressed in terms of specific heat capacities of the species participate in the chemical reactions, bracket integrals connected with the internal energy transfer in inelastic non-reactive collisions and energy transfer coefficients. Reactions of dissociation/recombination of homonuclear and heteronuclear diatomic molecules are considered. It is shown that all reaction rates are the complex functions of the species densities, similarly to the unimolecular reaction rates. For determining the rate coefficients it is recommended to tabulate corresponding bracket integrals, additionally to the equilibrium rate constants. Correlation of the obtained results with the irreversible thermodynamics is established.

  2. Ultrahigh reactivity and grave nanotoxicity of copper nanoparticles

    International Nuclear Information System (INIS)

    Huan Meng; Zhen Chen; Chengcheng Zhang; Yun Wang; Yuliang Zhao

    2007-01-01

    Recently, it was reported that the toxicity of copper particles increases with the decrease of the particle size on a mass basis. To understand this phenomenon, inductively coupled plasma mass spectrometry (ICP-MS) techniques and in vitro chemical studies were carried out to explore how they produce toxicity in vivo. The results suggest that when the sizes of particles become small and down to a nanoscale, copper becomes extremely reactive in a simulative intracorporeal environment. The nanosized copper particles consume the hydrogen ions in stomach more quickly than micron ones. These processes further convert the copper nanoparticles into cupric ions whose toxicity is very high in vivo. (author)

  3. The evolution of the temperature field during cavity collapse in liquid nitromethane. Part II: reactive case

    Science.gov (United States)

    Michael, L.; Nikiforakis, N.

    2018-02-01

    This work is concerned with the effect of cavity collapse in non-ideal explosives as a means of controlling their sensitivity. The main objective is to understand the origin of localised temperature peaks (hot spots) which play a leading order role at the early stages of ignition. To this end, we perform two- and three-dimensional numerical simulations of shock-induced single gas-cavity collapse in liquid nitromethane. Ignition is the result of a complex interplay between fluid dynamics and exothermic chemical reaction. In the first part of this work, we focused on the hydrodynamic effects in the collapse process by switching off the reaction terms in the mathematical formulation. In this part, we reinstate the reactive terms and study the collapse of the cavity in the presence of chemical reactions. By using a multi-phase formulation which overcomes current challenges of cavity collapse modelling in reactive media, we account for the large density difference across the material interface without generating spurious temperature peaks, thus allowing the use of a temperature-based reaction rate law. The mathematical and physical models are validated against experimental and analytic data. In Part I, we demonstrated that, compared to experiments, the generated hot spots have a more complex topological structure and that additional hot spots arise in regions away from the cavity centreline. Here, we extend this by identifying which of the previously determined high-temperature regions in fact lead to ignition and comment on the reactive strength and reaction growth rate in the distinct hot spots. We demonstrate and quantify the sensitisation of nitromethane by the collapse of the isolated cavity by comparing the ignition times of nitromethane due to cavity collapse and the ignition time of the neat material. The ignition in both the centreline hot spots and the hot spots generated by Mach stems occurs in less than half the ignition time of the neat material. We compare

  4. Interaction phenomena at reactive metal/ceramic interfaces.

    Energy Technology Data Exchange (ETDEWEB)

    McDeavitt, S. M.; Billings, G. W.; Indacochea, J. E.

    2000-11-03

    The objective of this study was to understand the interface chemical reactions between stable ceramics and reactive liquid metals, and developing microstructure. Experiments were conducted at elevated temperatures where small metal samples of Zr and Zr-alloy were placed on top of selected oxide and non-oxide ceramic substrates (Y{sub 2}O{sub 3}, ZrN, ZrC, and HfC). The sample stage was heated in high-purity argon to about 2000 C, held in most cases for five minutes at the peak temperature, and then cooled to room temperature at {approximately}20 c/min. An external video camera was used to monitor the in-situ wetting and interface reactions. Post-test examinations of the systems were conducted by scanning electron microscopy and energy dispersive spectroscopy. It was determined that the Zr and the Zr-alloy are very active in the wetting of stable ceramics at elevated temperatures. In addition, in some systems, such as Zr/ZrN, a reactive transition phase formed between the ceramic and the metal. In other systems, such as Zr/Y{sub 2}O{sub 3}, Zr/ZrC and Zr/HfC, no reaction products formed, but a continuous and strong joint developed under these circumstances also.

  5. Comparison between the reactivity of coal and synthetic coal models

    Energy Technology Data Exchange (ETDEWEB)

    A. Arenillas; C. Pevida; F. Rubiera; J.J. Pis [Instituto Nacional del Carbon, CSIC, Oviedo (Spain)

    2003-10-01

    A mixture of carbon compounds was pyrolysed under an inert atmosphere at different temperatures in a fixed bed reactor. The resultant chars were characterised in terms of texture and thermal behaviour. Textural characterisation of the chars was carried out by N{sub 2} and CO{sub 2} adsorption isotherms at -196 and 0{sup o}C, respectively. Char isothermal reactivity in air at 500{sup o}C, and in CO{sub 2} at 1000{sup o}C, was performed in a thermogravimetric analyser (TGA). Temperature-programmed combustion tests under 20% oxygen in argon were also performed in the TGA linked to a mass spectrometer (TGA/MS). The results showed that char textural properties do not always relate well to their reactivity. Not only do physical properties (e.g. surface area, porosity) but also chemical properties (e.g. active sites concentration and distribution) play an important role in the reaction of carbonaceous material and oxidant. On the other hand, in terms of chemical composition the chars obtained from the mixture of carbon compounds were very similar to the chars produced under the same experimental conditions by a high volatile bituminous coal. The fact that carbon compounds are well known makes it easier to obtain knowledge about the functional groups present in synthetic char, and to study the mechanisms of heterogeneous reactions such as the reduction of NO with carbon. 13 refs., 8 figs., 3 tabs.

  6. A simple reactivity-meter system

    International Nuclear Information System (INIS)

    Ferreira, P.S.B.

    1992-01-01

    This paper describes a new version of a reactivity meter developed at the Institute of Nuclear Energy Research (IPEN) (Brazil). The reactivity meter computes the reactor reactivity utilizing a programmable electrometer that performs the data aquisition. The software commands the main functions of the electrometer, the data acquisition, data transfer, and reactivity calculation. The necessary hardware for this reactivity meter are a programmable electrometer, a microcomputer, and interfaces for the microcomputer to communicate with the electrometer. If it is necessary, it is possible to connect a graphic register to the microcomputer. With this conventional hardware, available in any nuclear reactor facility, one can build a powerful reactivity meter. Adding to these advantages, one can use the microcomputer on-line to analyze the data, store the data on diskettes, or create graphics

  7. Overview of the physical-chemical properties of the noble gases

    International Nuclear Information System (INIS)

    McKinley, C.

    1973-01-01

    This paper lists the concentrations of noble gases in the atmosphere and the relative abundance of the stable isotopes. Selected physical properties are tabulated; solubilities of noble gases in water and other liquids, and liquid-vapor equilibria data for binary systems containing a noble gas are presented. Adsorption data are tabulated for illustrative conventional adsorbents and are also presented by a Polanyi correlation. Clathration, biochemical effects, and chemical reactivity are highlighted. Analytical procedures are briefly described. Other relatively non-reactive gases present in the atmosphere in trace quantities are mentioned: methane, carbon tetrafluoride, and sulfur hexafluoride.

  8. A chemically inert drug can stimulate T cells in vitro by their T cell receptor in non-sensitised individuals

    International Nuclear Information System (INIS)

    Engler, Olivier B.; Strasser, Ingrid; Naisbitt, Dean J.; Cerny, Andreas; Pichler, Werner J.

    2004-01-01

    Drugs can interact with T cell receptors (TCR) after binding to peptide-MHC structures. This binding may involve the formation of a stable, covalent bond between a chemically reactive drug and MHC or the peptide embedded within. Alternatively, if the drug is chemically inert, the binding may be non-covalent and readily reversible. Both types of drug presentation account for a substantial number of adverse side effects to drugs. Presently no tests are available to predict the ability of chemically inert drugs to stimulate an immune response. Here we present data on the successful induction of a primary T cell immune response in vitro against a chemically inert drug using blood from healthy individuals, previously not exposed to the drug. Blood lymphocytes were stimulated by the chemically inert drug sulfamethoxazole and the protein-reactive drug-metabolite sulfamethoxazole-nitroso in the presence of IL-2. 9/10 individuals reacted in response to sulfamethoxazole-nitroso, but only three reacted to the chemically inert compound sulfamethoxazole. Drug reactive T cells could be detected after 14-35 days of cell culture by drug-specific proliferation or cytotoxicity, which was MHC-restricted. These cells were CD4, CD8 positive or CD4/CD8 double positive and T cell clones generated secreted Th0 type cytokines. Drug interaction lead to down-regulation of specific TCR. These data confirm the ability of chemically inert drugs to stimulate certain T cells by their TCR and may provide the opportunity to screen new drugs for their ability to interact with TCRs

  9. Growth and characterization of nitrogen-doped TiO2 thin films prepared by reactive pulsed laser deposition

    International Nuclear Information System (INIS)

    Sauthier, G.; Ferrer, F.J.; Figueras, A.; Gyoergy, E.

    2010-01-01

    Nitrogen-doped titanium dioxide (TiO 2 ) thin films were grown on (001) SiO 2 substrates by reactive pulsed laser deposition. A KrF* excimer laser source (λ = 248 nm, τ FWHM ≅ 10 ns, ν = 10 Hz) was used for the irradiations of pressed powder targets composed by both anatase and rutile phase TiO 2 . The experiments were performed in a controlled reactive atmosphere consisting of oxygen or mixtures of oxygen and nitrogen gases. The obtained thin film crystal structure was investigated by X-ray diffraction, while their chemical composition as well as chemical bonding states between the elements were studied by X-ray photoelectron spectroscopy. An interrelation was found between nitrogen concentration, crystalline structure, bonding states between the elements, and the formation of titanium oxinitride compounds. Moreover, as a result of the nitrogen incorporation in the films a continuous red-shift of the optical absorption edge accompanied by absorption in the visible spectral range between 400 and 500 nm wavelength was observed.

  10. Reactivity of rhodium during co-deposition of rhodium and carbon

    International Nuclear Information System (INIS)

    Marot, Laurent; Steiner, Roland; De Temmerman, Gregory; Oelhafen, Peter

    2009-01-01

    The detailed characterizations of rhodium/carbon films prepared by co-deposition using a dual magnetron sputtering have been carried out on silicon substrates at room temperature. Effects of the carbon incorporated in the film on the chemical bonding state, optical reflectivity and crystallinity were investigated using XPS, reflectivity measurements, XRD and SEM. The incorporation of carbon changes the films' crystallinity and thus producing amorphous films. The reflectivity of the films decreases linearly as the rhodium concentration decreases. It is important to note that no chemical bonding was observed between rhodium and carbon whatever the deposition conditions, even at high deposition temperature. Concerning the reactivity of rhodium films with oxygen, after long term storage in air the rhodium surface is covered with a thin rhodium oxide (few nanometers). However, for these films no variation of the optical reflectivity was observed after long air storage.

  11. An experimental study of steam explosions involving chemically reactive metal

    International Nuclear Information System (INIS)

    Cho, D.H.; Armstrong, D.R.; Gunther, W.H.; Basu, S.

    1997-01-01

    An experimental study of molten zirconium-water explosions was conducted. A 1-kg mass of zirconium melt was dropped into a column of water. Explosions took place only when an external trigger was used. In the triggered tests, the extent of oxidation of the zirconium melt was very extensive. However, the explosion energetics estimated were found to be very small compared to the potential chemical energy available from the oxidation reaction. Zirconium is of particular interest, since it is a component of the core materials of the current nuclear power reactors. This paper describes the test apparatus and summarizes the results of four tests conducted using pure zirconium melt

  12. Chemical Functionalization of Graphene Family Members

    Science.gov (United States)

    Vacchi, Isabella Anna; Ménard-Moyon, Cécilia; Bianco, Alberto

    2017-01-01

    Thanks to their outstanding physicochemical properties, graphene and its derivatives are interesting nanomaterials with a high potential in several fields. Graphene, graphene oxide, and reduced graphene oxide, however, differ partially in their characteristics due to their diverse surface composition. Those differences influence the chemical reactivity of these materials. In the following chapter the reactivity and main functionalization reactions performed on graphene, graphene oxide, and reduced graphene oxide are discussed. A part is also dedicated to the main analytical techniques used for characterization of these materials. Functionalization of graphene and its derivatives is highly important to modulate their characteristics and design graphene-based conjugates with novel properties. Functionalization can be covalent by forming strong and stable bonds with the graphene surface, or non-covalent via π-π, electrostatic, hydrophobic, and/or van der Waals interactions. Both types of functionalization are currently exploited.

  13. Evaluation of mast cell counts and microvessel density in reactive lesions of the oral cavity

    Directory of Open Access Journals (Sweden)

    Maryam Kouhsoltani

    2016-12-01

    Full Text Available Background. Reliable immunohistochemical assays to assess the definitive role of mast cells (MCs and angiogenesis in the pathogenesis of oral reactive lesions are generally not available. The aim of the present study was to evaluate mast cell counts (MCC and microvessel density (MVD in oral reactive lesions and determine the correlation between MCC and MVD. Methods. Seventy-five cases of reactive lesions of the oral cavity, including pyogenic granuloma, fibroma, peripheral giant cell granuloma, inflammatory fibrous hyperplasia, peripheral ossifying fibroma (15 for each category were immunohisto-chemically stained with MC tryptase and CD31. Fifteen cases of normal gingival tissue were considered as the control group. The mean MCC and MVD in superficial and deep connective tissues were assessed and total MCC and MVD was computed for each lesion. Results. Statistically significant differences were observed in MCC and MVD between the study groups (P < 0.001. MC tryptase and CD31 expression increased in the superficial connective tissue of each lesion in comparison to the deep con-nective tissue. A significant negative correlation was not found between MCC and MVD in oral reactive lesions (P < 0.001, r = -0.458. Conclusion. Although MCs were present in the reactive lesions of the oral cavity, a direct correlation between MCC and MVD was not found in these lesions. Therefore, a significant interaction between MCs and endothelial cells and an active role for MCs in the growth of oral reactive lesions was not found in this study.

  14. Chemical ageing and transformation of diffusivity in semi-solid multi-component organic aerosol particles

    Science.gov (United States)

    Pfrang, C.; Shiraiwa, M.; Pöschl, U.

    2011-07-01

    Recent experimental evidence underlines the importance of reduced diffusivity in amorphous semi-solid or glassy atmospheric aerosols. This paper investigates the impact of diffusivity on the ageing of multi-component reactive organic particles approximating atmospheric cooking aerosols. We apply and extend the recently developed KM-SUB model in a study of a 12-component mixture containing oleic and palmitoleic acids. We demonstrate that changes in the diffusivity may explain the evolution of chemical loss rates in ageing semi-solid particles, and we resolve surface and bulk processes under transient reaction conditions considering diffusivities altered by oligomerisation. This new model treatment allows prediction of the ageing of mixed organic multi-component aerosols over atmospherically relevant timescales and conditions. We illustrate the impact of changing diffusivity on the chemical half-life of reactive components in semi-solid particles, and we demonstrate how solidification and crust formation at the particle surface can affect the chemical transformation of organic aerosols.

  15. Chemical ageing and transformation of diffusivity in semi-solid multi-component organic aerosol particles

    Directory of Open Access Journals (Sweden)

    C. Pfrang

    2011-07-01

    Full Text Available Recent experimental evidence underlines the importance of reduced diffusivity in amorphous semi-solid or glassy atmospheric aerosols. This paper investigates the impact of diffusivity on the ageing of multi-component reactive organic particles approximating atmospheric cooking aerosols. We apply and extend the recently developed KM-SUB model in a study of a 12-component mixture containing oleic and palmitoleic acids. We demonstrate that changes in the diffusivity may explain the evolution of chemical loss rates in ageing semi-solid particles, and we resolve surface and bulk processes under transient reaction conditions considering diffusivities altered by oligomerisation. This new model treatment allows prediction of the ageing of mixed organic multi-component aerosols over atmospherically relevant timescales and conditions. We illustrate the impact of changing diffusivity on the chemical half-life of reactive components in semi-solid particles, and we demonstrate how solidification and crust formation at the particle surface can affect the chemical transformation of organic aerosols.

  16. Transport Properties of a Kinetic Model for Chemical Reactions without Barriers

    International Nuclear Information System (INIS)

    Alves, Giselle M.; Kremer, Gilberto M.; Soares, Ana Jacinta

    2011-01-01

    A kinetic model of the Boltzmann equation for chemical reactions without energy barrier is considered here with the aim of evaluating the reaction rate and characterizing the transport coefficient of shear viscosity for the reactive system. The Chapman-Enskog solution of the Boltzmann equation is used to compute the chemical reaction effects, in a flow regime for which the reaction process is close to the final equilibrium state. Some numerical results are provided illustrating that the considered chemical reaction without energy barrier can induce an appreciable influence on the reaction rate and on the transport coefficient of shear viscosity.

  17. A Coupled Chemical and Mass Transport Model for Concrete Durability

    DEFF Research Database (Denmark)

    Jensen, Mads Mønster; Johannesson, Björn; Geiker, Mette Rica

    2012-01-01

    In this paper a general continuum theory is used to evaluate the service life of cement based materials, in terms of mass transport processes and chemical degradation of the solid matrix. The model established is a reactive mass transport model, based on an extended version of the Poisson-Nernst-...

  18. Reactive Force Field for Liquid Hydrazoic Acid with Applications to Detonation Chemistry

    Science.gov (United States)

    Furman, David; Dubnikova, Faina; van Duin, Adri; Zeiri, Yehuda; Kosloff, Ronnie

    The development of a reactive force field (ReaxFF formalism) for Hydrazoic acid (HN3), a highly sensitive liquid energetic material, is reported. The force field accurately reproduces results of density functional theory (DFT) calculations. The quality and performance of the force field are examined by detailed comparison with DFT calculations related to uni, bi and trimolecular thermal decomposition routes. Reactive molecular dynamics (RMD) simulations are performed to reveal the initial chemical events governing the detonation chemistry of liquid HN3. The outcome of these simulations compares very well with recent results of tight-binding DFT molecular dynamics and thermodynamic calculations. Based on our RMD simulations, predictions were made for the activation energies and volumes in a broad range of temperatures and initial material compressions. Work Supported by The Center of Excellence for Explosives Detection, Mitigation and Response, Department of Homeland Security.

  19. Coal structure and reactivity changes induced by chemical demineralisation

    Energy Technology Data Exchange (ETDEWEB)

    Rubiera, F.; Arenillas, A.; Pevida, C.; Garcia, R.; Pis, J.J. [Department of Energy and Environment, Instituto Nacional del Carbon, CSIC, Apartado 73, 33080 Oviedo (Spain); Steel, K.M.; Patrick, J.W. [Fuel Technology Group, School of Chemical, Environmental and Mining Engineering, Nottingham University, University Park, NG7 2RD Nottingham (United Kingdom)

    2002-12-01

    The aim of this work was to determine the influence that an advanced demineralisation procedure has on the combustion characteristics of coal. A high-volatile bituminous coal with 6.2% ash content was treated in a mixture of hydrofluoric and fluorosilicic acids (HF/H{sub 2}SiF{sub 6}). Nitric acid was used either as a pretreatment, or as a washing stage after HF/H{sub 2}SiF{sub 6} demineralisation, with an ash content as low as 0.3% being attained in the latter case. The structural changes produced by the chemical treatment were evaluated by comparison of the FTIR spectra of the raw and treated coal samples. The devolatilisation and combustibility behaviour of the samples was studied by using a thermobalance coupled to a mass spectrometer (TGA-MS) for evolved gas analysis. The combustibility characteristics of the cleaned samples were clearly improved, there being a decrease in SO{sub 2} emissions.

  20. Production of chemically reactive radioactive ion beams through on-line separation

    International Nuclear Information System (INIS)

    Joinet, A.

    2003-10-01

    The ISOL (isotope separation on line) allows the production of secondary radioactive ion beams through spallation or fragmentation or fission reactions that take place in a thick target bombarded by a high intensity primary beam. The challenge is to increase the intensity and purity of the radioactive beam. The optimization of the system target/source requires the right choice of material for the target by taking into account the stability of the material, its reactivity and the ionization method used. The target is an essential part of the system because radioactive elements are generated in it and are released more or less quickly. Tests have been made in order to select the best fitted material for the release of S, Se, Te, Ge and Sn. Materials tested as target filling are: ZrO 2 , Nb, Ti, V,TiO 2 , CeO x , ThO 2 , C, ZrC 4 and VC). Other molecules such as: COSe, COS, SeS, COTe, GeS, SiS, SnS have been studied to ease the extraction of recoil nuclei (Se, S, Te, Ge and Sn) produced inside the target

  1. A Tariff for Reactive Power

    Energy Technology Data Exchange (ETDEWEB)

    Kueck, John D [ORNL; Kirby, Brendan J [ORNL; Li, Fangxing [ORNL; Tufon, Christopher [Pacific Gas and Electric Company; Isemonger, Alan [California Independent System Operator

    2008-07-01

    Two kinds of power are required to operate an electric power system: real power, measured in watts, and reactive power, measured in volt-amperes reactive or VARs. Reactive power supply is one of a class of power system reliability services collectively known as ancillary services, and is essential for the reliable operation of the bulk power system. Reactive power flows when current leads or lags behind voltage. Typically, the current in a distribution system lags behind voltage because of inductive loads such as motors. Reactive power flow wastes energy and capacity and causes voltage droop. To correct lagging power flow, leading reactive power (current leading voltage) is supplied to bring the current into phase with voltage. When the current is in phase with voltage, there is a reduction in system losses, an increase in system capacity, and a rise in voltage. Reactive power can be supplied from either static or dynamic VAR sources. Static sources are typically transmission and distribution equipment, such as capacitors at substations, and their cost has historically been included in the revenue requirement of the transmission operator (TO), and recovered through cost-of-service rates. By contrast, dynamic sources are typically generators capable of producing variable levels of reactive power by automatically controlling the generator to regulate voltage. Transmission system devices such as synchronous condensers can also provide dynamic reactive power. A class of solid state devices (called flexible AC transmission system devices or FACTs) can provide dynamic reactive power. One specific device has the unfortunate name of static VAR compensator (SVC), where 'static' refers to the solid state nature of the device (it does not include rotating equipment) and not to the production of static reactive power. Dynamic sources at the distribution level, while more costly would be very useful in helping to regulate local voltage. Local voltage regulation would

  2. INFLUENCE OF GROUNDWATER GEOCHEMISTRY ON THE LONG-TERM PERFORMANCE OF IN-SITU PERMEABLE REACTIVE BARRIERS CONTAINING ZERO-VALENT IRON

    Science.gov (United States)

    Reactive barriers that couple subsurface fluid flow with a passive chemical treatment zone are emerging, cost effective approaches for in-situ remediation of contaminated groundwater. Factors such as the build-up of surface precipitates, bio-fouling, and changes in subsurface tr...

  3. Geochemical reactivity of subsurface sediments as potential buffer to anthropogenic inputs: A strategy for regional characterization in the Netherlands

    NARCIS (Netherlands)

    Gaans, P.F.M. van; Griffioen, J.; Mol, G.; Klaver, G.

    2011-01-01

    Purpose: Sedimentary aquifers are prone to anthropogenic disturbance. Measures aimed at mitigation or adaptation require sound information on the reactivity of soil/sediments towards the infiltrating water, as this determines the chemical quality of the groundwater and receiving surface waters.

  4. Geochemical reactivity of subsurface sediments as potential buffer to anthropogenic inputs: a strategy for regional characterization in the Netherlands

    NARCIS (Netherlands)

    van Gaans, P.F.M.; Griffioen, J.; Mol, Gerben; Klaver, G.T.

    2011-01-01

    Purpose Sedimentary aquifers are prone to anthropogenic disturbance. Measures aimed at mitigation or adaptation require sound information on the reactivity of soil/sediments towards the infiltrating water, as this determines the chemical quality of the groundwater and receiving surface waters. Here,

  5. Phase behavior and reactive transport of partial melt in heterogeneous mantle model

    Science.gov (United States)

    Jordan, J.; Hesse, M. A.

    2013-12-01

    The reactive transport of partial melt is the key process that leads to the chemical and physical differentiation of terrestrial planets and smaller celestial bodies. The essential role of the lithological heterogeneities during partial melting of the mantle is increasingly recognized. How far can enriched melts propagate while interacting with the ambient mantle? Can the melt flow emanating from a fertile heterogeneity be localized through a reactive infiltration feedback in a model without exogenous factors or contrived initial conditions? A full understanding of the role of heterogeneities requires reactive melt transport models that account for the phase behavior of major elements. Previous work on reactive transport in the mantle focuses on trace element partitioning; we present the first nonlinear chromatographic analysis of reactive melt transport in systems with binary solid solution. Our analysis shows that reactive melt transport in systems with binary solid solution leads to the formation of two separate reaction fronts: a slow melting/freezing front along which enthalpy change is dominant and a fast dissolution/precipitation front along which compositional changes are dominated by an ion-exchange process over enthalpy change. An intermediate state forms between these two fronts with a bulk-rock composition and enthalpy that are not necessarily bounded by the bulk-rock composition and enthalpy of either the enriched heterogeneity or the depleted ambient mantle. The formation of this intermediate state makes it difficult to anticipate the porosity changes and hence the stability of reaction fronts. Therefore, we develop a graphical representation for the solution that allows identification of the intermediate state by inspection, for all possible bulk-rock compositions and enthalpies of the heterogeneity and the ambient mantle. We apply the analysis to the partial melting of an enriched heterogeneity. This leads to the formation of moving precipitation

  6. Chemical equilibrium and reaction modeling of arsenic and selenium in soils

    Science.gov (United States)

    The chemical processes and soil factors that affect the concentrations of As and Se in soil solution were discussed. Both elements occur in two redox states differing in toxicity and reactivity. Methylation and volatilization reactions occur in soils and can act as detoxification pathways. Precip...

  7. Automatized Assessment of Protective Group Reactivity: A Step Toward Big Reaction Data Analysis.

    Science.gov (United States)

    Lin, Arkadii I; Madzhidov, Timur I; Klimchuk, Olga; Nugmanov, Ramil I; Antipin, Igor S; Varnek, Alexandre

    2016-11-28

    We report a new method to assess protective groups (PGs) reactivity as a function of reaction conditions (catalyst, solvent) using raw reaction data. It is based on an intuitive similarity principle for chemical reactions: similar reactions proceed under similar conditions. Technically, reaction similarity can be assessed using the Condensed Graph of Reaction (CGR) approach representing an ensemble of reactants and products as a single molecular graph, i.e., as a pseudomolecule for which molecular descriptors or fingerprints can be calculated. CGR-based in-house tools were used to process data for 142,111 catalytic hydrogenation reactions extracted from the Reaxys database. Our results reveal some contradictions with famous Greene's Reactivity Charts based on manual expert analysis. Models developed in this study show high accuracy (ca. 90%) for predicting optimal experimental conditions of protective group deprotection.

  8. Chemical Kinetic Models for Advanced Engine Combustion

    Energy Technology Data Exchange (ETDEWEB)

    Pitz, William J. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Mehl, Marco [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Westbrook, Charles K. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

    2014-10-22

    The objectives for this project are as follows: Develop detailed chemical kinetic models for fuel components used in surrogate fuels for compression ignition (CI), homogeneous charge compression ignition (HCCI) and reactivity-controlled compression-ignition (RCCI) engines; and Combine component models into surrogate fuel models to represent real transportation fuels. Use them to model low-temperature combustion strategies in HCCI, RCCI, and CI engines that lead to low emissions and high efficiency.

  9. Reactive Programming in Java

    CERN Document Server

    CERN. Geneva

    2017-01-01

    Reactive Programming in gaining a lot of excitement. Many libraries, tools, and frameworks are beginning to make use of reactive libraries. Besides, applications dealing with big data or high frequency data can benefit from this programming paradigm. Come to this presentation to learn about what reactive programming is, what kind of problems it solves, how it solves them. We will take an example oriented approach to learning the programming model and the abstraction.

  10. Simulation of reactive nanolaminates using reduced models: II. Normal propagation

    Energy Technology Data Exchange (ETDEWEB)

    Salloum, Maher; Knio, Omar M. [Department of Mechanical Engineering, The Johns Hopkins University, Baltimore, MD 21218-2686 (United States)

    2010-03-15

    Transient normal flame propagation in reactive Ni/Al multilayers is analyzed computationally. Two approaches are implemented, based on generalization of earlier methodology developed for axial propagation, and on extension of the model reduction formalism introduced in Part I. In both cases, the formulation accommodates non-uniform layering as well as the presence of inert layers. The equations of motion for the reactive system are integrated using a specially-tailored integration scheme, that combines extended-stability, Runge-Kutta-Chebychev (RKC) integration of diffusion terms with exact treatment of the chemical source term. The detailed and reduced models are first applied to the analysis of self-propagating fronts in uniformly-layered materials. Results indicate that both the front velocities and the ignition threshold are comparable for normal and axial propagation. Attention is then focused on analyzing the effect of a gap composed of inert material on reaction propagation. In particular, the impacts of gap width and thermal conductivity are briefly addressed. Finally, an example is considered illustrating reaction propagation in reactive composites combining regions corresponding to two bilayer widths. This setup is used to analyze the effect of the layering frequency on the velocity of the corresponding reaction fronts. In all cases considered, good agreement is observed between the predictions of the detailed model and the reduced model, which provides further support for adoption of the latter. (author)

  11. Modern integral equation techniques for quantum reactive scattering theory

    International Nuclear Information System (INIS)

    Auerbach, S.M.

    1993-11-01

    Rigorous calculations of cross sections and rate constants for elementary gas phase chemical reactions are performed for comparison with experiment, to ensure that our picture of the chemical reaction is complete. We focus on the H/D+H 2 → H 2 /DH + H reaction, and use the time independent integral equation technique in quantum reactive scattering theory. We examine the sensitivity of H+H 2 state resolved integral cross sections σ v'j',vj (E) for the transitions (v = 0,j = 0) to (v' = 1,j' = 1,3), to the difference between the Liu-Siegbahn-Truhlar-Horowitz (LSTH) and double many body expansion (DMBE) ab initio potential energy surfaces (PES). This sensitivity analysis is performed to determine the origin of a large discrepancy between experimental cross sections with sharply peaked energy dependence and theoretical ones with smooth energy dependence. We find that the LSTH and DMBE PESs give virtually identical cross sections, which lends credence to the theoretical energy dependence

  12. Reactivity estimation during a reactivity-initiated accident using the extended Kalman filter

    International Nuclear Information System (INIS)

    Busquim e Silva, R.; Marques, A.L.F.; Cruz, J.J.; Shirvan, K.; Kazimi, M.S.

    2015-01-01

    Highlights: • The EKF is modeled using sophisticate strategies to make the algorithm robust and accurate. • For a supercritical reactor under RIA, the EKF presents better results compared to IPK method independent of magnitude of the noise loads. • A sensitivity for five distinct carry-over effects indicates that the EKF is less sensitive to the different set of noise. • Although the P3D/R5 simulates the reactivity using a spatial kinetics method, the use of PKRE to model the EKF provides accurate results. • The reactivity’s standard deviation is higher for the IKF method. • Under HZP (slow power response) the IPK reactivity varies widely from positive to negative values (add extra difficulty to controlling the supercritical reactor): the EKF method does not have similar behavior under the same conditions (better controlling the operation). - Abstract: This study implements the extended Kalman filter (EKF) to estimate the nuclear reactor reactivity behavior under a reactivity-initiated accident (RIA). A coupled neutronics/thermal hydraulics code PARCS/RELAP5 (P3D/R5) simulates a control rod assembly ejection (CRE) on a traditional 2272 MWt PWR to generate the reactor power profile. A MATLAB script adds random noise to the simulated reactor power. For comparison, the inverse point kinetics (IPK) deterministic method is also implemented. Three different cases of CRE are simulated and the EKF, IPK and the P3D/R5 reactivity are compared. It was found that the EKF method presents better results compared to the IPK method. Furthermore, under a RIA due to small reactivity insertion and slow power response, the IPK reactivity varies widely from positive to negative, which may add extra difficulty to the task of controlling a supercritical reactor. This feature is also confirmed by a sensitivity analysis for five different noise loads and three distinct noise measurements standard deviations (SD)

  13. Regarding KUR Reactivity Measurement System

    International Nuclear Information System (INIS)

    Nakamori, Akira; Hasegawa, Kei; Tsuchiyama, Tatsuo; Yamamoto, Toshihiro; Okumura, Ryo; Sano, Tadafumi

    2012-01-01

    This article reported: (1) the outline of the reactivity measurement system of Kyoto University Research Reactor (KUR), (2) the calibration data of control rod, (3) the problems and the countermeasures for range switching of linear output meter. For the laptop PC for the reactivity measurement system, there are four input signals: (1) linear output meter, (2) logarithmic output meter, (3) core temperature gauge, and (4) control rod position. The hardware of reactivity measurement system is controlled with Labview installed on the laptop. Output, reactivity, reactor period, and the change in reactivity due to temperature effect or Xenon effect are internally calculated and displayed in real-time with Labview based on the four signals above. Calculation results are recorded in the form of a spreadsheet. At KUR, the reactor core arrangement was changed, so the control rod was re-calibrated. At this time, calculated and experimental values of reactivity based on the reactivity measurement system were compared, and it was confirmed that the reactivity calculation by Labview was accurate. The range switching of linear output meter in the nuclear instrumentation should automatically change within the laptop, however sometimes this did not function properly in the early stage. It was speculated that undefined percent values during the transition of percent value were included in the calculation and caused calculation errors. The range switching started working properly after fixing this issue. (S.K.)

  14. Cardiovascular reactivity and proactive and reactive relational aggression among women with and without a history of sexual abuse.

    Science.gov (United States)

    Murray-Close, Dianna; Rellini, Alessandra H

    2012-01-01

    This study examined the association between cardiovascular reactivity and proactive and reactive functions of relational aggression among women with and without a history of sexual abuse. Heart rate reactivity, blood pressure reactivity, and respiratory sinus arrhythmia reactivity while recounting a relational stressor (e.g., being left out) were assessed. Participants provided self-reports of relational aggression and a history of sexual abuse prior to age 16. Results indicated that cardiovascular reactivity was only associated with relational aggression among women with a history of sexual abuse. In addition, whereas blunted reactivity was associated with proactive relational aggression, exaggerated reactivity was associated with reactive relational aggression. These findings highlight the importance of considering contextual moderators of the association between cardiovascular reactivity and aggression; moreover, results highlight distinct cardiovascular correlates of different functions of aggression. Finally, the findings underscore the need for additional research examining the physiological correlates of aggressive behavior among women. Copyright © 2011 Elsevier B.V. All rights reserved.

  15. Time space domain decomposition methods for reactive transport - Application to CO2 geological storage

    International Nuclear Information System (INIS)

    Haeberlein, F.

    2011-01-01

    Reactive transport modelling is a basic tool to model chemical reactions and flow processes in porous media. A totally reduced multi-species reactive transport model including kinetic and equilibrium reactions is presented. A structured numerical formulation is developed and different numerical approaches are proposed. Domain decomposition methods offer the possibility to split large problems into smaller subproblems that can be treated in parallel. The class of Schwarz-type domain decomposition methods that have proved to be high-performing algorithms in many fields of applications is presented with a special emphasis on the geometrical viewpoint. Numerical issues for the realisation of geometrical domain decomposition methods and transmission conditions in the context of finite volumes are discussed. We propose and validate numerically a hybrid finite volume scheme for advection-diffusion processes that is particularly well-suited for the use in a domain decomposition context. Optimised Schwarz waveform relaxation methods are studied in detail on a theoretical and numerical level for a two species coupled reactive transport system with linear and nonlinear coupling terms. Well-posedness and convergence results are developed and the influence of the coupling term on the convergence behaviour of the Schwarz algorithm is studied. Finally, we apply a Schwarz waveform relaxation method on the presented multi-species reactive transport system. (author)

  16. Reactivity of silicon and germanium doped CNTs toward aromatic sulfur compounds: A theoretical approach

    International Nuclear Information System (INIS)

    Galano, Annia; Francisco-Marquez, Misaela

    2008-01-01

    Adsorption processes of thiophene and benzothiophene on pristine carbon nanotubes (CNTs), and on CNTs doped with Si or Ge, have been modeled with Density Functional. This is the first study on the chemical reactivity of such doped tubes. The calculated data suggest that the presence of silicon or germanium atoms in CNTs increases their reactivity toward thiophene, and benzothiophene. The adsorption of these species on pristine CNTs seems very unlikely to occur, while the addition products involving doped CNTs were found to be very stable, with respect to the isolated reactants, in terms of Gibbs free energy. Several of these adsorption processes were found to be significantly exergonic (ΔG < 0) in non-polar liquid phase. The results reported in this work suggest that Si and Ge defects on CNTs increase their reactivity toward unsaturated species, and could make them useful in the removal processes of aromatic sulfur compounds from oil-hydrocarbons. However, according to our results, CNTs doped with Si atoms are expected to be more efficient as aromatic sulfur compounds scavengers than those doped with Ge. These results also suggest that the presence of silicon and germanium atoms in the CNTs structures enhances their reactivity toward nucleophilic molecules, compared to pristine carbon nanotubes

  17. Optimal allocation of SVC and TCSC using quasi-oppositional chemical reaction optimization for solving multi-objective ORPD problem

    Directory of Open Access Journals (Sweden)

    Susanta Dutta

    2018-05-01

    Full Text Available This paper presents an efficient quasi-oppositional chemical reaction optimization (QOCRO technique to find the feasible optimal solution of the multi objective optimal reactive power dispatch (RPD problem with flexible AC transmission system (FACTS device. The quasi-oppositional based learning (QOBL is incorporated in conventional chemical reaction optimization (CRO, to improve the solution quality and the convergence speed. To check the superiority of the proposed method, it is applied on IEEE 14-bus and 30-bus systems and the simulation results of the proposed approach are compared to those reported in the literature. The computational results reveal that the proposed algorithm has excellent convergence characteristics and is superior to other multi objective optimization algorithms. Keywords: Quasi-oppositional chemical reaction optimization (QOCRO, Reactive power dispatch (RPD, TCSC, SVC, Multi-objective optimization

  18. Enhancement of chemically induced reactive oxygen species production and DNA damage in human SH-SY5Y neuroblastoma cells by 872 MHz radiofrequency radiation

    Energy Technology Data Exchange (ETDEWEB)

    Luukkonen, Jukka [Department of Environmental Science, University of Kuopio, Bioteknia 2, P.O. Box 1627, FI-70211 Kuopio (Finland)], E-mail: Jukka.Luukkonen@uku.fi; Hakulinen, Pasi; Maeki-Paakkanen, Jorma [Department of Environmental Health, National Public Health Institute, P.O. Box 95, FI-70701 Kuopio (Finland); Juutilainen, Jukka; Naarala, Jonne [Department of Environmental Science, University of Kuopio, Bioteknia 2, P.O. Box 1627, FI-70211 Kuopio (Finland)

    2009-03-09

    The objective of the study was to investigate effects of 872 MHz radiofrequency (RF) radiation on intracellular reactive oxygen species (ROS) production and DNA damage at a relatively high SAR value (5 W/kg). The experiments also involved combined exposure to RF radiation and menadione, a chemical inducing intracellular ROS production and DNA damage. The production of ROS was measured using the fluorescent probe dichlorofluorescein and DNA damage was evaluated by the Comet assay. Human SH-SY5Y neuroblastoma cells were exposed to RF radiation for 1 h with or without menadione. Control cultures were sham exposed. Both continuous waves (CW) and a pulsed signal similar to that used in global system for mobile communications (GSM) mobile phones were used. Exposure to the CW RF radiation increased DNA breakage (p < 0.01) in comparison to the cells exposed only to menadione. Comparison of the same groups also showed that ROS level was higher in cells exposed to CW RF radiation at 30 and 60 min after the end of exposure (p < 0.05 and p < 0.01, respectively). No effects of the GSM signal were seen on either ROS production or DNA damage. The results of the present study suggest that 872 MHz CW RF radiation at 5 W/kg might enhance chemically induced ROS production and thus cause secondary DNA damage. However, there is no known mechanism that would explain such effects from CW RF radiation but not from GSM modulated RF radiation at identical SAR.

  19. Enhancement of chemically induced reactive oxygen species production and DNA damage in human SH-SY5Y neuroblastoma cells by 872 MHz radiofrequency radiation

    International Nuclear Information System (INIS)

    Luukkonen, Jukka; Hakulinen, Pasi; Maeki-Paakkanen, Jorma; Juutilainen, Jukka; Naarala, Jonne

    2009-01-01

    The objective of the study was to investigate effects of 872 MHz radiofrequency (RF) radiation on intracellular reactive oxygen species (ROS) production and DNA damage at a relatively high SAR value (5 W/kg). The experiments also involved combined exposure to RF radiation and menadione, a chemical inducing intracellular ROS production and DNA damage. The production of ROS was measured using the fluorescent probe dichlorofluorescein and DNA damage was evaluated by the Comet assay. Human SH-SY5Y neuroblastoma cells were exposed to RF radiation for 1 h with or without menadione. Control cultures were sham exposed. Both continuous waves (CW) and a pulsed signal similar to that used in global system for mobile communications (GSM) mobile phones were used. Exposure to the CW RF radiation increased DNA breakage (p < 0.01) in comparison to the cells exposed only to menadione. Comparison of the same groups also showed that ROS level was higher in cells exposed to CW RF radiation at 30 and 60 min after the end of exposure (p < 0.05 and p < 0.01, respectively). No effects of the GSM signal were seen on either ROS production or DNA damage. The results of the present study suggest that 872 MHz CW RF radiation at 5 W/kg might enhance chemically induced ROS production and thus cause secondary DNA damage. However, there is no known mechanism that would explain such effects from CW RF radiation but not from GSM modulated RF radiation at identical SAR

  20. Reactive nitrogen deposition to South East Asian rainforest

    Science.gov (United States)

    di Marco, Chiara F.; Phillips, Gavin J.; Thomas, Rick; Tang, Sim; Nemitz, Eiko; Sutton, Mark A.; Fowler, David; Lim, Sei F.

    2010-05-01

    Deposition Network to estimate the total annual atmospheric reactive nitrogen deposition to this tropical forest ecosystem and to quantify the relative contribution of the different chemical compounds.